Rechargeable battery cell

ABSTRACT

This disclosure relates to a rechargeable battery cell, comprising:an active metal;at least one positive electrode;at least one negative electrode comprising an active material selected from the group consisting of an insertion material made of carbon, an alloy-forming active material, an intercalation material which does not comprise carbon, and a conversion active material;an SO2 based electrolyte comprising a first conducting salt which has the formula (I),wherein:M is a metal selected from the group consisting of alkali metals, alkaline earth metals, metals of group 12 of the periodic table of the elements, and aluminum;x is an integer from 1 to 3;R1, R2, R3 and R4 are selected independently of one another from the group consisting of C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl, C6-C14 aryl and C5-C14 heteroaryl; andZ is aluminum or boron.

RELATED APPLICATIONS

This application is a continuation of PCT/EP2020/071566, filed Jul. 30, 2020, which claims priority to EP 19 189 435.1, filed Jul. 31, 2019, the entire disclosures of both of which are hereby incorporated herein by reference.

BACKGROUND

This disclosure relates to a rechargeable battery cell having an SO₂-based electrolyte.

Rechargeable battery cells are of great importance in many technical fields. They are often used for applications which require only small rechargeable battery cells having relatively low current intensities, for example, for the operation of cell phones. In addition, there is also a great need for larger rechargeable battery cells for high-energy applications, with mass storage of energy in the form of battery cells being of particular importance for the electric propulsion of vehicles.

High energy density is an important requirement for these types of rechargeable battery cells. This means that the rechargeable battery cell should comprise as much electrical energy as possible per unit weight and volume. Lithium has proven to be particularly advantageous as an active metal for this purpose. The active metal of a rechargeable battery cell is the metal whose ions within the electrolyte migrate to the negative or positive electrode when the cell is being charged or discharged and participate in electrochemical processes there. These electrochemical processes lead directly or indirectly to the release of electrons into the external circuit or to the absorption of electrons from the external circuit. Rechargeable battery cells comprising lithium as an active metal are also referred to as lithium-ion cells. The energy density of these lithium-ion cells can either be increased by increasing the specific capacity of the electrodes or by increasing the cell voltage.

Both the positive and negative electrodes of lithium-ion cells are designed as insertion electrodes. The term “insertion electrode” in the sense of this disclosure refers to electrodes which have a crystal structure into which ions of the active material can be stored and removed during operation of the lithium-ion cell. This means that the electrode processes can take place not only on the surface of the electrodes, but also within the crystalline structure. When charging the lithium-ion cell, the ions of the active metal are removed from the positive electrode and stored in the negative electrode. The reverse process takes place when the lithium-ion cell is discharged.

The electrolyte is also an important functional element of every rechargeable battery cell. It usually comprises a solvent or a solvent blend and at least one conducting salt. Solid electrolytes or ionic liquids, for example, do not comprise a solvent, but only a conducting salt. The electrolyte is in contact with the positive and negative electrodes of the battery cell. At least one ion of the conducting salt (anion or cation) is sufficiently mobile in the electrolyte such that a charge transport between the electrodes, required for the functioning of the rechargeable battery cell, can take place through ionic conduction. The electrolyte is oxidatively electrochemically decomposed from a certain upper cell voltage of the rechargeable battery cell. This process often leads to an irreversible destruction of the electrolyte components, and thus to a failure of the rechargeable battery cell. Reductive processes can also decompose the electrolyte when falling below a certain cell voltage. In order to avoid these processes, the positive and negative electrodes are chosen such that the cell voltage is below or above the decomposition voltage of the electrolyte. The electrolyte thus determines the voltage window, in the range of which a rechargeable battery cell can be operated reversibly, that is, repeatedly charged and discharged.

The lithium-ion cells known from the prior art comprise an electrolyte consisting of an organic solvent or solvent blend and a conducting salt dissolved therein. The conducting salt is a lithium salt such as lithium hexafluorophosphate (LiPF₆). The solvent blend can comprise, for example, ethylene carbonate. The electrolyte LP57, which has the composition 1 M LiPF₆ in EC (ethylene carbonate): EMC (ethyl methyl carbonate) 3:7 is an example of such an electrolyte. Due to the organic solvent or solvent blend, these kinds of lithium ion cells are also referred to as organic lithium-ion cells.

The negative electrode of these organic lithium-ion cells consists of a carbon coating which is applied to a discharge element made of copper. The discharge element provides the electronically conductive connection required between the carbon coating and the external circuit. The associated positive electrode consists of lithium cobalt oxide (LiCoO₂), which is applied to a discharge element made of aluminum. Both electrodes typically have a thickness of less than 100 μm and are therefore very thin.

It has long been known that unintentional overcharging of organic lithium ion cells leads to the irreversible decomposition of electrolyte components. The oxidative decomposition of the organic solvent and/or the conducting salt takes place on the surface of the positive electrode. The reaction heat generated during this decomposition and the resulting gaseous products are responsible for the subsequent so-called “thermal runaway” and the resulting destruction of the organic lithium ion cell. The vast majority of charging protocols for these organic lithium-ion cells use the cell voltage as an indicator of the end of charging. Accidents caused by a thermal runaway are particularly likely to occur when using multi-cell battery packs in which a plurality of organic lithium-ion cells having dissimilar capacities are connected in series.

Lithium is the most electronegative metal (−3.10 V vs. standard hydrogen electrode, SHE) and consequently all materials are reductively reacted thereto, for example, also organic electrolytes of the organic lithium-ion cells. This reductive decomposition of the organic electrolyte on the negative electrode is irreversible. No organic solvents are thermodynamically stable with respect to lithium or with respect to lithium which is stored in carbon (Li_(x)C₆). However, many solvents form a passivation film on the electrode surface of the negative electrode. This film spatially separates the solvent from the electrode, but is ionically conductive and thus enables the passage of lithium ions. The passivation film, the so-called “Solid Electrolyte Interphase” (SEI), gives stability to the system, by which the production of organic lithium-ion cells is made possible. Lithium is integrated into the passivation film during the formation of the SEI. This process is irreversible, whereby a loss of capacity is observed. This irreversible loss of capacity, which is also referred to as the coating layer capacity, depends on the electrolyte formulation and the electrodes used. In organic lithium-ion cells, the electrolyte decomposition and formation of lithium-ion-comprising layers often continues during further operation of the organic lithium-ion cell and is responsible for the loss of capacity and thus for a shorter service life of the organic lithium-ion cell. Capacity losses can also occur during the storage of charged organic lithium-ion cells. This so-called self-discharge can be based on both irreversible processes, such as electrolyte decomposition, and reversible processes in which the lithium stored in the negative electrode is transferred to the electrolyte solution and is available again the next time it is charged.

Organic lithium-ion cells are therefore problematic in terms of their stability and long-term operational reliability. Safety risks are also caused in particular by the flammability of the organic solvent or solvent blend. When an organic lithium-ion cell catches fire or even explodes, the organic solvent in the electrolyte forms a combustible material. Additional measures must be taken to avoid such safety risks. These measures include, in particular, a very precise regulation of the charging and discharging processes of the organic lithium-ion cell and an optimized battery design. Furthermore, the organic lithium-ion cell comprises components which melt in the event of an unintentional increase in temperature and can thereby flood the organic lithium-ion cell with molten plastic. A further uncontrolled increase in temperature is thus prevented. However, these measures lead to increased production costs in the manufacture of the organic lithium-ion cell and to an increased volume and weight. Furthermore, these measures reduce the energy density of the organic lithium-ion cell.

A further disadvantage of organic lithium-ion cells is that any hydrolysis products produced in the presence of residual amounts of water are very aggressive towards the cell components of the rechargeable battery cell. For example, the conducting salt LiPF₆, which is often used in organic cells, produces very reactive, aggressive hydrogen fluoride (HF) through reaction with traces of water. Because of this, when manufacturing such rechargeable battery cells having an organic electrolyte, attention must be paid to minimizing the residual water content comprised in the electrolyte and the cell components. Production therefore often takes place in costly drying rooms under extremely low humidity. The issues described above regarding stability and long-term operational reliability are of particular importance for the development of organic lithium-ion cells, which, on the one hand, are characterized by a high energy and power density level, and, on the other hand, by a very high degree of operational reliability and a very long service life, including a particularly high number of usable charge and discharge cycles.

A further development known from prior art therefore provides for the use of an electrolyte based on sulfur dioxide (SO₂) instead of an organic electrolyte for rechargeable battery cells. Rechargeable battery cells, which comprise an SO₂-based electrolyte, exhibit, among other things, high ionic conductivity. The term “SO₂-based electrolyte” refers to an electrolyte which comprises SO₂ not merely as an additive at low concentrations, but in which the mobility of the ions in the conducting salt, which is comprised in the electrolyte and which causes the charge transport, is at least in part, largely or even completely ensured by SO₂. The SO₂ thus serves as a solvent for the conducting salt. The conducting salt can form a liquid solvate complex with the gaseous SO₂, whereby the SO₂ is bound and the vapor pressure is noticeably reduced compared to the pure SO₂. Electrolytes having low vapor pressure are produced. Compared to the organic electrolytes described above, these SO₂-based electrolytes have the advantage of being non-combustible. Safety risks, which might occur due to the electrolyte's flammability, can thus be excluded.

For example, EP 2 290 738 B1 [V1] describes an SO₂-based electrolyte having the composition LiAlCl₄*SO₂ in combination with a negative electrode made of graphite and a positive electrode made of lithium cobalt oxide (LiCoO₂). A negative aspect of the battery cell is the formation of a coating layer on the graphite in the first cycle of the battery cell and thus a loss of capacity. Paragraph [0008] of [V1] states, in translation, that

-   -   “[ . . . ] a high proportion of the lithium comprised in the         positive electrode before the start of the charging process (for         example, approx. 25%) [ . . . ] is consumed during the first         charging process for the formation of the coating layer.”

In [V1], this problem is solved by the active metal required for the formation of the coating layer being transferred from an additional supply to one of the electrodes.

A disadvantage that also occurs, among other things, with these SO₂-based electrolytes is that any hydrolysis products formed in the presence of residual amounts of water react with the cell components of the rechargeable battery cell and thus lead to the formation of undesired by-products. Because of this, in the manufacture of such rechargeable battery cells having an SO₂-based electrolytes, attention should be paid to minimizing the residual water content comprised in the electrolyte and the cell components.

A further problem with the SO₂-based electrolytes is that many conducting salts, in particular also known for organic lithium-ion cells, are not soluble in SO₂. Measurements showed that SO₂ is a poor solvent for many conducting salts, such as lithium fluoride (LiF), lithium bromide (LiBr), lithium sulfate (Li₂SO₄), lithium bis(oxalato)borate (LiBOB), lithium hexafluoroarsenate (LiAsF₆), lithium tetrafluoroborate (LiBF₄), trilithium hexafluoroaluminate (Li₃AlF₆), lithium hexafluoroantimonate (LiSbF₆), lithium difluoro(oxalato)borate (LiBF₂C₂O₄), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium metaborate (LiBO₂), lithium aluminate (LiAlO₂), lithium triflate (LiCF₃SO₃) and lithium chlorosulfonate (LiSO₃Cl). The solubility of these conducting salts in SO₂ is approx. 10⁻²-10⁻⁴ mol/L (see Table 1). With these low salt concentrations, it can be assumed that there are at most only low conductivities, which are not sufficient for the useful operation of a rechargeable battery cell.

TABLE 1 Solubility of Various Conducting Salts in SO₂ Solubility/ Solubility/ Conducting Salt mol/L in SO₂ Conducting Salt mol/L in SO₂ LiF 2.1 · 10⁻³ LiPF₆ 1.5 · 10⁻² LiBr 4.9 · 10⁻³ LiSbF₆ 2.8 · 10⁻⁴ Li₂SO₄ 2.7 · 10⁻⁴ LiBF₂(C₂O₄) 1.4 · 10⁻⁴ LiB(C₂O₄)₂ 3.2 · 10⁻⁴ CF₃SO₂NLiSO₂CF₃ 1.5 · 10⁻² Li₃PO₄ — LiBO₂ 2.6 · 10⁻⁴ Li₃AlF₆ 2.3 · 10⁻³ LiAlO₂ 4.3 · 10⁻⁴ LiBF₄ 1.7 · 10⁻³ LiCF₃SO₃ 6.3 · 10⁻⁴ LiAsF₆ 1.4 · 10⁻³

In order to further improve the possible uses and properties of rechargeable battery cells that comprise an SO₂-based electrolyte, the object of this disclosure is to specify a rechargeable battery cell having an SO₂-based electrolyte, which, compared to the rechargeable battery cells known from the prior art:

-   -   has a wide electrochemical window, so that no oxidative         electrolyte decomposition occurs at the positive electrode;     -   has a stable coating layer on the negative electrode, whereby         the coating layer capacity should be low and no further         reductive electrolyte decomposition should occur on the negative         electrode during further operation;     -   comprises an SO₂-based electrolyte which exhibits good         solubility for conducting salts and is therefore a good ion         conductor and electronic insulator, so that ion transport can be         facilitated and self-discharge can be reduced to a minimum;     -   comprises an SO₂-based electrolyte that is also inert to other         components of the rechargeable battery cell, such as separators,         electrode materials and cell packaging materials,     -   is resistant against various misuses such as electrical,         mechanical or thermal;     -   comprises an SO₂-based electrolyte, which exhibits an increased         stability against residual amounts of water in the cell         components of rechargeable battery cells;     -   exhibits improved electrical performance data, in particular         high energy density;     -   exhibits improved overcharging and deep discharging and less         self-discharge and     -   shows an increased service life, in particular a high number of         usable charge and discharge cycles.

Such rechargeable battery cells should, in particular, also have very good electrical energy and performance data, high operational reliability and service life, in particular a large number of usable charge and discharge cycles, without the electrolyte decomposing during operation of the rechargeable battery cell.

This object is solved by a rechargeable battery cell having the features of claim 1. Claims 2 to 30 describe advantageous developments of the rechargeable battery cell according to this disclosure.

A rechargeable battery cell according to this disclosure comprises an active metal, at least one positive electrode, at least one negative electrode, a housing and an electrolyte. The negative electrode comprises an active material selected from the group formed by:

-   -   an insertion material made of carbon,     -   an alloy-forming active material,     -   an intercalation material that does not comprise carbon, and     -   a conversion active material.

The electrolyte is based on SO₂ and comprises at least one first conducting salt. Said first conducting salt has the formula (I).

In formula (I), M is a metal selected from the group formed by alkali metals, alkaline earth metals, metals of group 12 of the periodic table of the elements and aluminum. x is an integer from 1 to 3. The substituents R¹, R², R³ and R⁴ are selected independently of one another from the group formed by C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₂-C₁₀ alkynyl, C₃-C₁₀ cycloalkyl, C₆-C₁₄ aryl and C₅-C₁₄ heteroaryl. The central atom Z is either aluminum or boron.

In the sense of this disclosure, the term “insertion materials made of carbon” refers to materials made of the element carbon which have a structure into which ions of the active metal can be stored and removed during operation of the lithium-ion cell. This means that the electrode processes can take place not only on the surface of the electrodes, but also within the structure. If, for example, a conducting salt based on lithium is used, then lithium ions can be stored in the insertion material while the rechargeable battery cell is being charged and can be removed therefrom while the rechargeable battery cell is being discharged.

The alloy-forming active materials are generally metals and metal alloys and their oxides which form an alloy with the active metal, such as lithium, for example, wherein this alloy formation takes place in or on the negative electrode and is essentially reversible. In contrast to insertion materials, the active metal in the alloys is not stored in an existing structure. Rather, the active metal is stored via phase change processes which, for example, when using lithium as an active metal, can lead to a lithium-comprising, binary end product. The active material can expand when the alloy is formed.

In the sense of this disclosure, the term “intercalation compound” refers to a sub-category of the insertion materials described above. Said intercalation compound acts as a host matrix, which has vacancies that are interconnected. The ions of the active metal can diffuse into these vacancies during the discharge process of the rechargeable battery cell and can be stored there. During the deposition of the ions of the active metal, only minor or no structural changes occur in the host matrix.

Conversion active materials undergo a chemical conversion or transformation during the electrode processes, which leads to the reversible formation of a chemical bond between the active metal and the active material.

The SO₂-based electrolyte used in the rechargeable battery cell according to this disclosure comprises SO₂ not only as an additive in low concentration, but in concentrations at which the mobility of the ions of the first conducting salt, which is comprised in the electrolyte and causes the charge transport, is at least partially, largely or even completely ensured by the SO₂. The first conducting salt is dissolved in the electrolyte and shows very good solubility therein. It can form a liquid solvate complex with the gaseous SO₂, in which the SO₂ is bound. In this case, the vapor pressure of the liquid solvate complex is noticeably reduced compared to the pure SO₂, producing electrolytes that have a low vapor pressure. However, it is also within the scope of this disclosure that, depending on the chemical structure of the first conducting salt according to formula (I), no reduction in vapor pressure can occur in the production of the electrolyte according to this disclosure. In the last-mentioned case, it is preferred for the production of the electrolyte according to this disclosure to be carried out at low temperature or under pressure. The electrolyte may also comprise a plurality of conducting salts of the formula (I), which differ from one another in their chemical structure.

In the sense of this disclosure, the term “C₁-C₁₀ alkyl” includes linear or branched saturated hydrocarbon groups having one to ten carbon atoms. These include, in particular, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, 2,2-dimethylpropyl, n-hexyl, iso-hexyl, 2-ethylhexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl and the like.

In the sense of this disclosure, the term “C₂-C₁₀ alkenyl” includes unsaturated linear or branched hydrocarbon groups having two to ten carbon atoms, wherein the hydrocarbon groups have at least one C—C double bond. These include, in particular, ethenyl, 1-propenyl, 2-propenyl, 1-n-butenyl, 2-n-butenyl, isobutenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, 1-decenyl and the like.

In the sense of this disclosure, the term “C₂-C₁₀ alkynyl” includes unsaturated linear or branched hydrocarbon groups having two to ten carbon atoms, wherein the hydrocarbon groups have at least one C—C triple bond. This includes, in particular, ethynyl, 1-propynyl, 2-propynyl, 1-n-butynyl, 2-n-butynyl, isobutynyl, 1-pentynyl, 1-hexynyl, 1-heptynyl, 1-octynyl, 1-nonynyl, 1-decynyl, and the like.

In the sense of this disclosure, the term “C₃-C₁₀ cycloalkyl” includes cyclic, saturated hydrocarbon groups having three to ten carbon atoms. These include, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexyl, cyclononyl and cyclodecanyl.

In the sense of this disclosure, the term “C₆-C₁₄ aryl” includes aromatic hydrocarbon groups having six to fourteen ring carbon atoms. This includes, in particular, phenyl (C₆H₅ group), naphthyl (C₁₀H₇ group) and anthracyl (C₁₄H₉ group).

In the sense of this disclosure, the term “C₅-C₁₄ heteroaryl” includes aromatic hydrocarbon groups having five to fourteen ring hydrocarbon atoms in which at least one hydrocarbon atom is replaced by a nitrogen, oxygen or sulfur atom. These include, in particular, pyrrolyl, furanyl, thiophenyl, pyrridinyl, pyranyl, thiopyranyl and the like. All of the hydrocarbon groups mentioned above are each bonded to the central atom according to formula (I) via the oxygen atom.

A rechargeable battery cell having such an electrolyte has the advantage over rechargeable battery cells having electrolytes known from the prior art in that the first conducting salt comprised therein has higher oxidation stability and consequently shows essentially no decomposition at higher cell voltages. Said electrolyte is resistant to oxidation, preferably at least up to an upper potential of 4.0 volts, preferably at least up to an upper potential of 4.4 volts, more preferably at least up to an upper potential of 4.8 volts, more preferably at least up to upper potential of 5.2 volts, more preferably at least up to an upper potential of 5.6 volts and most preferably at least up to an upper potential of 6.0 volts. Thus, when using such an electrolyte in a rechargeable battery cell, there is little or no electrolyte decomposition within the working potentials, that is, in the range between the end-of-charge voltage and the end-of-discharge voltage of both electrodes of the rechargeable battery cell. As a result, rechargeable battery cells according to this disclosure can have an end-of-charge voltage of at least 4.0 volts, more preferably of at least 4.4 volts, more preferably of at least 4.8 volts, more preferably of at least 5.2 volts, more preferably of at least 5.6 volts and most preferably of at least 6.0 volts.

The service life of the rechargeable battery cell comprising this electrolyte is significantly longer than that of rechargeable battery cells comprising electrolytes known from the prior art.

Furthermore, a rechargeable battery cell having such an electrolyte is also resistant to low temperatures. At a temperature of −40° C., for example, 61% of the charged capacity can still be discharged. The conductivity of the electrolyte at low temperatures is sufficient to operate a battery cell.

Furthermore, a rechargeable battery cell having such an electrolyte exhibits increased stability with respect to residual amounts of water. If there are still small residual amounts of water in the electrolyte (in the range of ppm), the electrolyte or the first conducting salt forms hydrolysis products with the water, which products, compared to the SO₂-based electrolytes known from the prior art, are significantly less aggressive towards the cell components. Because of this, the absence of water in the electrolyte plays a less important role in SO₂-based electrolytes in comparison to those known from the prior art. These advantages of the electrolyte according to this disclosure outweigh the disadvantage that arises from the fact that the first conducting salt according to formula (I) has a significantly larger anion size than the conducting salts known from the prior art. This higher anion size leads to a lower conductivity of the first conducting salt according to formula (I) compared to the conductivity of LiAlCl₄.

Negative Electrode

Advantageous developments of the rechargeable battery cell according to this disclosure with regard to the negative electrode are described below.

A first advantageous development of the rechargeable battery cell according to this disclosure provides that the negative electrode comprises anode active materials which form an alloy with lithium, in particular silicon. In other words, in its function as an active metal, lithium forms an alloy with the alloy-forming active material.

A further advantageous development of the rechargeable battery cell according to this disclosure provides that the insertion material made of carbon is selected from the group formed by graphite, natural graphite, synthetic graphite, graphitized mesocarbon microbeads (abbr.: MCMB), carbon-coated graphite and amorphous carbon. An insertion material made of the carbon allotrope graphite is preferred. Natural graphite can be designed flake-shaped (as a so-called flake conveyor) or rounded. Synthetic graphite, also known as graphitized carbon or electrographite, can be produced by graphitizing non-graphitic carbon, by chemical vapor deposition of hydrocarbons at temperatures above 2500 K, by the decomposition of chemically unstable carbides or by crystallization from carbon-supersaturated metal melts and, due to its more uniform structure and higher purity compared to natural graphites, among other things, can be preferably used as anode material. Graphitized mesocarbon microbeads (MCMB) preferably have an almost spherical structure having a diameter of, for example, 1-40 μm and consequently a low specific surface area. Mesocarbon microbeads are included among the so-called “soft carbon.” It is within the scope of this disclosure that the use of carbon fibers, such as mesophase pitch-based carbon fibers (abbr.: MCF) or vapor grown carbon fibers (abbr.: VGCF) can be provided as possible active materials for the negative electrode. The aforementioned amorphous carbon has no long-range crystalline order. Examples of this are graphitizable (soft carbon) and non-graphitizable (hard carbon) carbon.

A further advantageous development of the rechargeable battery cell according to this disclosure provides that the alloy-forming active material is selected from the group formed by lithium-storing metals and metal alloys or from the group formed by oxides of lithium-storing metals and metal alloys. These preferably include silicon (Si), in particular nano-silicon, μm-silicon, silicon nanofibers, germanium (Ge), tin (Sn), SnCo_(x)C_(y), SnSi_(x), and the like, and their oxides such as SnO_(x), SiO_(x), oxide glasses of Sn and Si and the like. Oxides of the composition MO_(x), in which M represents the metal, such as SiO_(x), for example, consist of a blend of the element and its oxides. SiO_(x) consists, for example, of a blend of the constituents Si, SiO and SiO₂. The weight proportions of the individual components can vary. Theoretical capacities of some of these alloy-forming anode active materials are specified in Table 2 below.

TABLE 2 Theoretical Capacities of Alloy-Forming Anode Active Materials Compared with Graphite Graph- Metal ite Li Si Ge Al Sn Lithium- LiC6 Li Li22Si5 Li22Ge5 AlLi Li22Sn5 Comprising Compound Theoretical 372 >3800 >3000 1600 993 994 Capacity (mAh · g−1)

A further advantageous development of the rechargeable battery cell according to this disclosure provides that the alloy-forming anode active material is a silicon-based anode active material. Such a material has a very high theoretical capacity.

A further advantageous development of the rechargeable battery cell according to this disclosure provides that the alloy-forming active material is formed from silicon or from silicon oxides or from blends of silicon and silicon oxides.

Anode active materials based on silicon can, for example, be classified into 0D , 1D, 2D and 3D materials according to their particle geometry or morphology. The 0D silicon materials include, for example, silicon nanoparticles having a particle size <150 nm, which can expand during electrochemical cycling without showing any damage. 1D nanorods, nanowires and nanotubes made of silicon offer good conductivity along the 1D transport channel due to the fact that they are usually connected directly to the current conductor in the electrode assembly. The group of 2D silicon materials includes, for example, thin films and nanoplates made of silicon, which generally have a high capacity. Herein, it is observed that the reversible capacity and the electrochemical cycle stability increase with decreasing layer thickness. 3D Si-based porous structures and networks can accommodate the volumetric changes due to their porous character and thus maintain their structural integrity. At the same time, these materials have a higher tap density and thus theoretically higher volumetric capacities than nanostructures of lower dimensionality.

A further advantageous development of the rechargeable battery cell according to this disclosure provides that the anode active materials which form an alloy with lithium comprise lithium even before use in a battery cell. This so-called pre-lithiation reduces the capacity losses, for example, due to the formation of the coating layer in the first cycle.

A further advantageous development of the rechargeable battery cell according to this disclosure provides that the negative electrode comprises at least one alloy-forming anode active material, in particular at least one anode active material which forms an alloy with lithium, in combination with at least one insertion material made of carbon. Combinations of silicon and/or silicon oxides and graphite are preferred. This includes, for example, composites that form mechanically stable bonds. The materials are embedded in one another. The combination can also take place in the form of loose mixtures, so-called blends. For example, silicon and graphite or SiO_(x) and graphite can be combined.

In a further advantageous development of the rechargeable battery cell according to this disclosure, the negative electrode comprises lithium-intercalation anode active materials that do not comprise carbon, such as lithium titanates (for example, Li₄Ti₅O₁₂).

In a further advantageous development of the rechargeable battery cell according to this disclosure, the anode active material is a conversion active material selected:

-   -   from the group formed by manganese oxides (MnO_(x)), iron oxides         (FeO_(x)), cobalt oxides (CoO_(x)), nickel oxides (NiO_(x)),         copper oxides (CuO_(x)), or     -   from the group formed by magnesium hydride (MgH₂), titanium         hydride (TiH₂), aluminum hydride (AlH₃) and boron-, aluminum-         and magnesium-based ternary hydrides         and the like.

A further advantageous development of the rechargeable battery cell according to this disclosure provides that the negative electrode is porous, wherein the porosity is preferably at most 50%, more preferably at most 45%, more preferably at most 40%, more preferably at most 35%, more preferably at most 30%, more preferably at most 20% and most preferably at most 10%. The porosity represents the cavity volume in relation to the total volume of the negative electrode, wherein the cavity volume is formed by so-called pores or cavities. This porosity leads to an increase in the inner surface area of the negative electrode. Furthermore, the porosity reduces the density of the negative electrode and thus also its weight. The individual pores of the negative electrode can preferably be completely filled with the electrolyte during operation.

A further advantageous development of the battery cell according to this disclosure provides that the negative electrode has a discharge element. This means that in addition to the active material or insertion material, the negative electrode also comprises a discharge element. This discharge element serves to enable the required electronically conductive connection of the active material of the negative electrode. For this purpose, the discharge element is in contact with the active material involved in the electrode reaction of the negative electrode. Said discharge element can be designed in a planar manner in the form of a thin metal sheet or a thin metal foil. The thin metal foil preferably has a perforated or mesh-like structure. The planar discharge element can also consist of a plastic film coated with metal. Said metal coatings have a thickness in the range from 0.1 μm to 20 μm. The active material of the negative electrode is preferably applied to the surface of the thin metal sheet, the thin metal foil or the metal-coated plastic foil. The active material can be applied to the front and/or the rear side of the planar discharge element. Such planar discharge elements have a thickness in the range from 5 μm to 50 μm. A thickness of the planar discharge element in the range from 10 μm to 30 μm is preferred. When using planar discharge elements, the negative electrode can have a total thickness of at least 20 μm, preferably at least 40 μm and particularly preferably at least 60 μm. The maximum thickness is at most 200 μm, preferably at most 150 μm and particularly preferably at most 100 μm. The area-specific capacity of the negative electrode based on the coating on one side is preferably at least 0.5 mAh/cm² when using a planar discharge element, wherein the following values are further preferred in this order: 1 mAh/cm², 3 mAh/cm², 5 mAh/cm², 10 mAh/cm², 15 mAh/cm², 20 mAh/cm².

Furthermore, there is also the possibility for the discharge element to be designed three-dimensionally in the form of a porous metal structure, in particular in the form of a metal foam. The term “three-dimensional porous metal structure” refers to any structure consisting of metal that not only extends over the length and width of the flat electrode like the thin metal sheet or the metal foil, but also over its thickness dimension. The three-dimensional porous metal structure is sufficiently porous such that the active material of the negative electrode can be incorporated into the pores of the metal structure. The amount of active material incorporated or applied is the loading on the negative electrode. When the discharge element is designed three-dimensionally in the form of a porous metal structure, in particular in the form of a metal foam, then the negative electrode preferably has a thickness of at least 0.2 mm, more preferably at least 0.3 mm, more preferably at least 0.4 mm, more preferably at least 0.5 mm and most preferably at least 0.6 mm. In this case, the thickness of the electrodes is significantly greater compared to negative electrodes, which is the case with organic lithium-ion cells. A further advantageous embodiment provides that the area-specific capacity of the negative electrode when using a three-dimensional discharge element, in particular in the form of a metal foam, is preferably at least 2.5 mAh/cm², wherein the following values are further preferred in this order: 5 mAh/cm², 15 mAh/cm², 25 mAh/cm², 35 mAh/cm², 45 mAh/cm², 55 mAh/cm², 65 mAh/cm², 75 mAh/cm². When the discharge element is designed three-dimensionally in the form of a porous metal structure, in particular in the form of a metal foam, the amount of active material of the negative electrode, that is, the loading of the electrode, based on its area, is at least 10 mg/cm², preferably at least 20 mg/cm², more preferably at least 40 mg/cm², more preferably at least 60 mg/cm², more preferably at least 80 mg/cm² and most preferably at least 100 mg/cm². This loading of the negative electrode has a positive effect on the charging process and the discharging process of the rechargeable battery cell.

In a further advantageous development of the battery cell according to this disclosure, the negative electrode has at least one binder. Said binder is preferably a fluorinated binder, in particular a polyvinylidene fluoride and/or a terpolymer which is formed from tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride. However, it can also be a binder which consists of a polymer which is composed of monomeric structural units of a conjugated carboxylic acid or of the alkali, alkaline earth or ammonium salt of this conjugated carboxylic acid or of a combination thereof. Furthermore, the binder can also consist of a polymer based on monomeric styrene and butadiene structural units. In addition, the binder can also be a binder from the group of carboxymethyl celluloses. The binder is present in the negative electrode, preferably in a concentration of at most 20% by weight, more preferably at most 15% by weight, more preferably at most 10% by weight, more preferably at most 7% by weight, more preferably at most 5% by weight and most preferably at most 2% by weight based on the total weight of the negative electrode.

In a further advantageous development of the battery cell according to this disclosure, the negative electrode has at least one conductivity additive. The conductivity additive should preferably have exhibit low weight, high chemical resistance and high specific surface area. Examples of conductivity additives are particulate carbon (carbon black, Super P, acetylene black), fibrous carbon (carbon nanotubes CNT, carbon (nano)fibers), finely divided graphites and graphene (nanosheets).

Electrolyte

Advantageous developments of the rechargeable battery cell with regard to the SO₂-based electrolyte are described below.

In a further advantageous embodiment of the rechargeable battery cells, the substituents R¹, R², R³ and R⁴ of the first conducting salt are selected independently of one another from the group formed by:

-   -   C₁-C₆ alkyl; preferably from C₂-C₄ alkyl; particularly         preferably from the alkyl groups 2-propyl, methyl and ethyl;     -   C₂-C₆ alkenyl; preferably from C₂-C₄ alkenyl; particularly         preferably from the alkenyl groups ethenyl and propenyl;     -   C₂-C₆ alkynyl; preferably from C₂-C₄ alkynyl;     -   C₃-C₆ cycloalkyl;     -   phenyl; and     -   C₅-C₇ heteroaryl.

In the case of this advantageous embodiment of the SO₂-based electrolyte, the term “C₁-C₆ alkyl” includes linear or branched saturated hydrocarbon groups having one to six hydrocarbon groups, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, 2,2-dimethylpropyl, n-hexyl and iso-hexyl. C₂-C₄ alkyls are preferred among these. The C₂-C₄ alkyls 2-propyl, methyl and ethyl are particularly preferred.

In the case of this advantageous embodiment of the SO₂-based electrolyte, the term “C₂-C₆ alkenyl” includes unsaturated linear or branched hydrocarbon groups having two to six carbon atoms, wherein the hydrocarbon groups have at least one C—C double bond. These include in particular ethenyl, 1-propenyl, 2-propenyl, 1-n-butenyl, 2-n-butenyl, isobutenyl, 1-pentenyl and 1-hexenyl, wherein C₂-C₄ alkenyls are preferred. Ethenyl and 1-propenyl are particularly preferred.

In the case of this advantageous embodiment of the SO₂-based electrolyte, the term “C₂-C₆ alkynyl” includes unsaturated linear or branched hydrocarbon groups having two to six carbon atoms, wherein the hydrocarbon groups have at least one C—C triple bond. These include in particular ethynyl, 1-propynyl, 2-propynyl, 1-n-butynyl, 2-n-butynyl, iso-butynyl, 1-pentynyl and 1-hexynyl. Preferred among these are C₂-C₄ alkynyls.

In the case of this advantageous embodiment of the SO₂-based electrolyte, the term “C₃-C₆ cycloalkyl” includes cyclic saturated hydrocarbon groups having three to six carbon atoms. These include in particular cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

In the case of this advantageous embodiment of the SO₂-based electrolyte, the term “C₅-C₇ heteroaryl” includes phenyl and naphthyl.

To improve the solubility of the first conducting salt in the SO₂-based electrolytes, the substituents R¹, R², R³ and R⁴ are substituted, in a further advantageous embodiment of the rechargeable battery cell, by at least one fluorine atom and/or by at least one chemical group, wherein the chemical group is selected from the group formed by C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, phenyl and benzyl. The chemical groups C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, phenyl and benzyl have the same properties or chemical structures as the hydrocarbon groups described above. Substituted in this context means that individual atoms or groups of atoms of the substituents R¹, R², R³ and R⁴ have been replaced by the fluorine atom and/or by the chemical group.

A particularly high solubility of the first conducting salt in the SO₂-based electrolytes can be achieved by at least one of the substituents R¹, R², R³ and R⁴ being a CF₃ group or an OSO₂CF₃ group.

In a further advantageous development of the rechargeable battery cell, the first conducting salt is selected from the group formed by:

In order to adjust the conductivity and/or other properties of the electrolyte to a desired value, the electrolyte in a further advantageous embodiment of the rechargeable battery cell according to this disclosure has at least one second conducting salt different from the first conducting salt according to formula (I). This means that, in addition to the first conducting salt, the electrolyte can comprise a or even further second conducting salts which differ from the first conducting salt in their chemical composition and their chemical structure.

In a further advantageous embodiment of the rechargeable battery cell according to this disclosure, the second conducting salt is an alkali metal compound, in particular a lithium compound. The alkali metal compound or the lithium compound are selected from the group formed by an aluminate, a halide, an oxalate, a borate, a phosphate, an arsenate and a gallate. The second conducting salt is preferably a lithium tetrahaloaluminate, in particular LiAlCl₄.

Furthermore, in a further advantageous embodiment of the rechargeable battery cell according to this disclosure, the electrolyte comprises at least one additive. This additive is preferably selected from the group formed by vinylene carbonate and its derivatives, vinylethylene carbonate and its derivatives, methylethylene carbonate and its derivatives, lithium (bisoxalato)borate, lithium difluoro(oxalato)borate, lithium tetrafluoro(oxalato)phosphate, lithium oxalate, 2-vinylpyridine, 4-vinylpyridine, cyclic exomethylene carbonates, sultones, cyclic and acyclic sulfonates, acyclic sulfites, cyclic and acyclic sulfinates, organic esters of inorganic acids, acyclic and cyclic alkanes, which acyclic and cyclic alkanes have a boiling point of at least 36° C. at 1 bar, aromatic compounds, halogenated cyclic and acyclic sulfonylimides, halogenated cyclic and acyclic phosphate esters, halogenated cyclic and acyclic phosphines, halogenated cyclic and acyclic phosphites, halogenated cyclic and acyclic phosphazenes, halogenated cyclic and acyclic silylamines, halogenated cyclic and acyclic halogenated esters, halogenated cyclic and acyclic amides, halogenated cyclic and acyclic anhydrides and halogenated organic heterocycles.

In relation to the total weight of the electrolyte composition, the electrolyte has the following composition in a further advantageous development of the rechargeable battery cell:

-   -   (i) 5 to 99.4% by weight sulfur dioxide,     -   (ii) 0.6 to 95% by weight of the first conducting salt,     -   (iii) 0 to 25% by weight of the second conducting salt and     -   (iv) 0 to 10% by weight of the additive.

As already mentioned above, the electrolyte can comprise not only a first conducting salt according to formula (I) and a second conducting salt, but also a plurality of first conducting salts according to formula (I) and a plurality of second conducting salts. In the last-mentioned case, the aforementioned percentages also include a plurality of first conducting salts and a plurality of second conducting salts. The molar concentration of the first conducting salt lies in the range from 0.01 mol/L to 10 mol/L, preferably from 0.05 mol/L to 10 mol/L, more preferably from 0.1 mol/L to 6 mol/L and most preferably from 0.2 mol/L to 3.5 mol/L, based on the total volume of the electrolyte.

A further advantageous development of the rechargeable battery cell according to this disclosure provides that the electrolyte comprises at least 0.1 mol SO₂, preferably at least 1 mol SO₂, more preferably at least 5 mol SO₂, more preferably at least 10 mol SO₂ and most preferably at least 20 mol SO₂ per mole of conducting salt. The electrolyte can also comprise very high molar proportions of SO₂, wherein the preferred upper limit value is 2600 mol SO₂ per mole of conducting salt and upper limits of 1500, 1000, 500 and 100 mol of SO₂ per mole of conducting salt are further preferred in this order. The term “per mole of conducting salt” refers to all conducting salts that are comprised in the electrolyte. Electrolytes based on SO₂ having such a concentration ratio between SO₂ and the conducting salt have the advantage in that they can dissolve a larger amount of conducting salt compared to the electrolytes known from the prior art, which are based, for example, on an organic solvent blend. In the context of this disclosure, it was found that, surprisingly, an electrolyte having a relatively low concentration of conducting salt is advantageous despite the associated higher vapor pressure, in particular with regard to its stability over many charge and discharge cycles of the rechargeable battery cell. The concentration of SO₂ in the electrolyte affects its conductivity. Thus, by choosing the SO₂ concentration, the conductivity of the electrolyte can be adjusted to the planned use of a rechargeable battery cell operated using this electrolyte.

The total content of SO₂ and the first conducting salt can be greater than 50 percent by weight (% by weight) of the weight of the electrolyte, preferably greater than 60% by weight, more preferably greater than 70% by weight, more preferably greater than 80% by weight, more preferably greater than 85% by weight, more preferably greater than 90% by weight, more preferably greater than 95% by weight or most preferably greater than 99% by weight.

The electrolyte can comprise at least 5% by weight SO₂ based on the total amount of the electrolyte comprised in the rechargeable battery cell, wherein values of 20% by weight SO₂, 40% by weight SO₂ and 60% by weight SO₂ are more preferred. The electrolyte can also comprise up to 95% by weight SO₂, wherein maximum values of 80% by weight SO₂ and 90% by weight SO₂ are preferred in this order.

It is within the scope of this disclosure for the electrolyte to preferably have only a small percentage or even no percentage of at least one organic solvent. The proportion of organic solvents in the electrolyte, which is present, for example, in the form of one solvent or a blend of a plurality of solvents, can preferably be at most 50% by weight of the weight of the electrolyte. Lower proportions of at most 40% by weight, at most 30% by weight, at most 20% by weight, at most 15% by weight, at most 10% by weight, at most 5% by weight or at most 1% by weight of the electrolyte weight are particularly preferred. More preferably, the electrolyte is free of organic solvents. Due to the low proportion of organic solvents or even their complete absence, the electrolyte is either hardly combustible or not at all combustible. This increases the operational safety of a rechargeable battery cell operated using such an SO₂-based electrolyte. The SO₂-based electrolyte is particularly preferably essentially free of organic solvents.

In relation to the total weight of the electrolyte composition, the electrolyte has the following composition in a further advantageous development of the rechargeable battery cell:

-   -   (i) 5 to 99.4% by weight sulfur dioxide,     -   (ii) 0.6 to 95% by weight of the first conducting salt,     -   (iii) 0 to 25% by weight of the second conducting salt,     -   (iv) 0 to 10% by weight of the additive and     -   (v) 0 to 50% by weight of an organic solvent.

Active Metal

Advantageous developments of the rechargeable battery cell according to this disclosure with regard to the active metal are described below.

In a first advantageous development of the rechargeable battery cell, the active metal is:

-   -   an alkali metal, in particular lithium or sodium;     -   an alkaline earth metal, in particular calcium;     -   a metal from group 12 of the periodic table, in particular zinc;         or     -   aluminum.

Positive Electrode

Advantageous developments of the rechargeable battery cell according to this disclosure with regard to the positive electrode are described below.

A first advantageous development of the rechargeable battery cell according to this disclosure provides that the positive electrode can be charged at least up to an upper potential of 4.0 volts, preferably up to a potential of 4.4 volts, more preferably of at least a potential of 4.8 volts, more preferably at least up to a potential of 5.2 volts, more preferably at least up to a potential of 5.6 volts and most preferably at least up to a potential of 6.0 volts.

In a further advantageous development of the rechargeable battery cell according to this disclosure, the positive electrode comprises at least one active material. Said material can store ions of the active metal and release and take up the ions of the active metal during operation of the battery cell.

In a further advantageous development of the rechargeable battery cell according to this disclosure, the positive electrode comprises at least one intercalation compound. In the sense of this disclosure, the term “intercalation compound” refers to a sub-category of the insertion materials described above. Said intercalation compound acts as a host matrix, which has vacancies that are interconnected. The ions of the active metal can diffuse into these vacancies during the discharge process of the rechargeable battery cell and can be stored there. During the deposition of the ions of the active metal, only minor or no structural changes occur in the host matrix.

In a further advantageous development of the rechargeable battery cell according to this disclosure, the positive electrode comprises at least one conversion compound as the active material. In the sense of this disclosure, the term “conversion compounds” refers to materials which form other materials during electrochemical activity; that is, chemical bonds are broken and re-established during charging and discharging of the battery cell. Structural changes occur in the matrix of the conversion compound during the absorption or release of the ions of the active metal.

In a further advantageous development of the rechargeable battery cell according to this disclosure, the active material has the composition A_(x)M′_(y)M″_(z)O_(a). In this composition, A_(x)M′_(y)M″_(z)O_(a):

-   -   A is at least one metal selected from the group formed by the         alkali metals, the alkaline earth metals, the metals of group 12         of the periodic table or aluminum,     -   M′ is at least one metal selected from the group formed by the         elements Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn;     -   M″ is at least one element selected from the group formed by the         elements of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,         15 and 16 of the periodic table of the elements;     -   x and y independently of one another are numbers greater than 0;     -   z is a number greater than or equal to 0; and     -   a is a number greater than 0.

A is preferably the metal lithium, that is, the compound can have the composition Li_(x)M′_(y)M″_(z)O_(a).

The indices y and z in the composition A_(x)M′_(y)M″_(z)O_(a), relate to the totality of metals and elements that are represented by M′ and M″, respectively. If, for example, M′ comprises two metals M′¹ and M′², the following applies to the index y: y=y1+y2, wherein y1 and y2 represent the indices of the metals M′¹ and M′². The indices x, y, z and a must be chosen such that there is charge neutrality within the composition. Examples of compounds in which M′ comprises two metals are lithium nickel manganese cobalt oxides of the composition Li_(x)Ni_(y1)Mn_(y2)Co_(z)O₂ with M′¹=Ni, M′²=Mn and M″=Co. Examples of compounds in which z=0, that is, which have no further metal or element M″, are lithium cobalt oxides Li_(x)Co_(y)O_(a). For example, if M″ comprises two elements, on the one hand, a metal M″¹ and on the other hand, phosphorus as M″², the following applies to the index z: z=z1+z2, wherein z1 and z2 represent the indices of the metal M″¹ and phosphorus (M″²). The indices x, y, z and a must be chosen such that there is charge neutrality within the composition. Examples of compounds in which A comprises lithium, M″ a metal M″¹ and phosphorus as M″² are lithium iron manganese phosphates Li_(x)Fe_(y)Mn_(z1)P_(z2)O₄ with A=Li, M′=Fe, M″¹=Mn and M″²=P and z2=1. In a further composition, M″ can comprise two non-metals, for example, fluorine as M″¹ and sulfur as M″². Examples of such compounds are lithium iron fluorosulfates Li_(x)Fe_(y)F_(z1)S_(z2)O₄ with A=Li, M′=Fe, M″₁=F and M″₂=P.

A further advantageous development of the rechargeable battery cell according to this disclosure provides that M′ consists of the metals nickel and manganese and M″ is cobalt. It can be compositions of the formula Li_(x)Ni_(y1)Mn_(y2)Co_(z)O₂ (NMC) thereby, that is, lithium nickel manganese cobalt oxide having the structure of layered oxides. Examples of these lithium nickel manganese cobalt oxide active materials are LiNi_(1/3)Mn_(1/3)Co_(1/3)O₂ (NMC111), LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂ (NMC622) and LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂ (NMC811). Further compounds of lithium nickel manganese cobalt oxide can have the composition LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂, LiNi_(0.5)Mn_(0.25)Co_(0.25)O₂, LiNi_(0.52)Mn_(0.32)Co_(0.16)O₂, LiNi_(0.55)Mn_(0.30)Co_(0.15)O₂, LiNi_(0.58)Mn_(0.14)Co_(0.28)O₂, LiNi_(0.64)Mn_(0.18)Co_(0.18)O₂, LiNi_(0.65)Mn_(0.27)Co_(0.08)O₂, LiNi_(0.7)Mn_(0.2)Co_(0.1)O₂, LiNi_(0.7)Mn_(0.15)Co_(0.15)O₂, LiNi_(0.72)Mn_(0.10)Co_(0.18)O₂, LiNi_(0.76)Mn_(0.14)Co_(0.10)O₂, LiNi_(0.86)Mn_(0.04)Co_(0.10)O₂, LiNi_(0.90)Mn_(0.05)Co_(0.05)O₂, LiNi_(0.95)Mn_(0.025)Co_(0.025)O₂ or a combination thereof. Positive electrodes for rechargeable battery cells having a cell voltage of over 4.6 volts can be produced using these compounds.

A further advantageous development of the rechargeable battery cell according to this disclosure provides that the active material is a metal oxide that is rich in lithium and manganese (lithium- and manganese-rich oxide material). Said metal oxide can have the composition Li_(x)Mn_(y)M″_(z)O_(a). In the formula Li_(x)M′_(y)M″_(z)O_(a) described above, M′ thus represents the metal manganese (Mn). The index x here is greater than or equal to 1, the index y is greater than the index z or greater than the sum of the indices z1+z2+z3 etc. For example, if M″ comprises two metals M″¹ and M″² with the indices z1 and z2 (for example, Li_(1.2)Mn_(0.525)Ni_(0.175)Co_(0.102) with M″¹=Ni z1=0.175 and M″²=Co z2=0.1), the following applies for the index y: y>z1+z2, The index z is greater than or equal to 0 and the index a is greater than 0. The indices x, y, z and a must be chosen such that there is charge neutrality within the composition. Metal oxides which are rich in lithium and manganese can also be described by the formula mLi₂MnO₃.(1−m)LiM′O₂ with 0<m<1. Examples of such compounds are Li_(1.2)Mn_(0.525)Ni_(0.175)Co_(0.1)O₂, Li_(1.2)Mn_(0.6)Ni_(0.2)O₂ or Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O₂.

A further advantageous development of the rechargeable battery cell according to this disclosure provides that the composition has the formula A_(x)M′_(y)M″_(z)O₄. These compounds are spinel structures. For example, A can be lithium, M′ cobalt, and M″ manganese. In this case, the active material is lithium cobalt manganese oxide (LiCoMnO₄). LiCoMnO₄ can be used to produce positive electrodes for rechargeable battery cells having a cell voltage of over 4.6 volts. This LiCoMnO₄ is preferably free of Mn³⁺. In a further example, M′ can be nickel and M″ can be manganese. In this case, the active material is lithium nickel manganese oxide (LiNiMnO₄). The molar proportions of the two metals M′ and M″ can vary. Lithium nickel manganese oxide can, for example, have the composition LiNi_(0.5)Mn_(1.5)O₄.

In a further advantageous development of the rechargeable battery cell according to this disclosure, the positive electrode comprises at least one active material which constitutes a conversion compound. Conversion compounds undergo a solid-state redox reaction during the absorption of the active metal, for example, lithium or sodium, in which the crystal structure of the material changes. This occurs by breaking and recombining chemical bonds. Completely reversible reactions of conversion compounds can be, for example, as follows:

$\begin{matrix} \left. {{MX_{z}} + {y\mspace{14mu}{Li}}}\leftrightarrow{M + {z\mspace{14mu}{Li}_{({y/z})}X}} \right. & {{Type}\mspace{14mu} A} \\ \left. {X + {y\mspace{14mu}{Li}}}\leftrightarrow{{Li}_{y}X} \right. & {{Type}\mspace{14mu} B} \end{matrix}$

Examples of conversion compounds are FeF₂, FeF₃, CoF₂, CuF₂, NiF₂, BiF₃, FeCl₃, FeCl₂, CoCl₂, NiCl₂, CuCl₂, AgCl, LiCl, S, Li₂S, Se, Li₂Se, Te, I and LiI.

In a further advantageous development, the compound has the composition A_(x)M′_(y)M″_(z1)M″_(z2)O₄, wherein M″ is phosphorus and z2 has the value 1. The compound having the composition Li_(x)M′_(y)M″_(z1)M″_(z2)O₄ is what are known as lithium metal phosphates. In particular, this compound has the composition Li_(x)Fe_(y)Mn_(z1)P_(z2)O₄. Examples of lithium metal phosphates are lithium iron phosphate (LiFePO₄) or lithium iron manganese phosphates (Li(Fe_(y)Mn_(z))PO₄). An example of a lithium iron manganese phosphate is the phosphate of the composition Li(Fe_(0.3)Mn_(0.7))PO₄. An example of a lithium iron manganese phosphate is the phosphate of the composition Li(Fe_(0.3)Mn_(0.7))PO₄. Lithium metal phosphates of other compositions can also be used for the battery cell according to this disclosure.

A further advantageous development of the rechargeable battery cell according to this disclosure provides that the positive electrode comprises at least one metal compound. This metal compound is selected from the group that is formed by a metal oxide, a metal halide and a metal phosphate. The metal of this metal compound is preferably a transition metal of the atomic numbers 22 to 28 of the periodic table of the elements, in particular cobalt, nickel, manganese or iron.

A further advantageous development of the rechargeable battery cell according to this disclosure provides that the positive electrode comprises at least one metal compound which has the chemical structure of a spinel, a layered oxide, a conversion compound or a polyanionic compound.

It is within the scope of this disclosure for the positive electrode to comprise at least one of the compounds described or a combination of the compounds as the active material. A combination of the compounds refers to a positive electrode which comprises at least two of the materials described.

A further advantageous development of the battery cell according to this disclosure provides that the positive electrode has a discharge element. This means that the positive electrode also comprises a discharge element in addition to the active material. Said discharge element serves to enable the required electronically conductive connection of the active material of the positive electrode. For this purpose, the discharge element is in contact with the active material involved in the electrode reaction of the positive electrode.

Said discharge element can be designed in a planar manner in the form of a thin metal sheet or a thin metal foil. The thin metal foil preferably has a perforated or mesh-like structure. The planar discharge element can also consist of a plastic film coated with metal. Said metal coatings have a thickness in the range from 0.1 μm to 20 μm. The active material of the positive electrode is preferably applied to the surface of the thin metal sheet, the thin metal foil or the metal-coated plastic foil. The active material can be applied to the front and/or the rear side of the planar discharge element. Such planar discharge elements have a thickness in the range from 5 μm to 50 μm. A thickness of the planar discharge element in the range from 10 μm to 30 μm is preferred. When using planar discharge elements, the positive electrode can have a total thickness of at least 20 μm, preferably at least 40 μm and particularly preferably at least 60 μm. The maximum thickness is at most 200 μm, preferably at most 150 μm and particularly preferably at most 100 μm. The area-specific capacity of the positive electrode based on the coating on one side is preferably at least 0.5 mAh/cm² when using a planar discharge element, wherein the following values are further preferred in this order: 1 mAh/cm², 3 mAh/cm², 5 mAh/cm², 10 mAh/cm², 15 mAh/cm², 20 mAh/cm².

Furthermore, there is also the possibility for the discharge element of the positive electrode to be designed three-dimensionally in the form of a porous metal structure, in particular in the form of a metal foam. The three-dimensional porous metal structure is sufficiently porous such that the active material of the positive electrode can be incorporated into the pores of the metal structure. The amount of active material incorporated or applied is the loading on the positive electrode. When the discharge element is designed three-dimensionally in the form of a porous metal structure, in particular in the form of a metal foam, then the positive electrode preferably has a thickness of at least 0.2 mm, more preferably at least 0.3 mm, more preferably at least 0.4 mm, more preferably at least 0.5 mm and most preferably at least 0.6 mm. A further advantageous embodiment provides that the area-specific capacity of the positive electrode when using a three-dimensional discharge element, in particular in the form of a metal foam, is preferably at least 2.5 mAh/cm², wherein the following values are further preferred in this order: 5 mAh/cm², 15 mAh/cm², 25 mAh/cm², 35 mAh/cm², 45 mAh/cm², 55 mAh/cm², 65 mAh/cm², 75 mAh/cm². When the discharge element is designed three-dimensionally in the form of a porous metal structure, in particular in the form of a metal foam, the amount of active material of the positive electrode, that is, the loading of the electrode, based on its area, is at least 10 mg/cm², preferably at least 20 mg/cm², more preferably at least 40 mg/cm², more preferably at least 60 mg/cm², more preferably at least 80 mg/cm² and most preferably at least 100 mg/cm². This loading of the positive electrode has a positive effect on the charging process and the discharging process of the rechargeable battery cell.

In a further advantageous development of the battery cell according to this disclosure, the positive electrode has at least one binder. Said binder is preferably a fluorinated binder, in particular a polyvinylidene fluoride and/or a terpolymer which is formed from tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride. However, it can also be a binder which consists of a polymer which is composed of monomeric structural units of a conjugated carboxylic acid or of the alkali, alkaline earth or ammonium salt of this conjugated carboxylic acid or of a combination thereof. Furthermore, the binder can also consist of a polymer based on monomeric styrene and butadiene structural units. In addition, the binder can also be a binder from the group of carboxymethyl celluloses. The binder is present in the positive electrode, preferably in a concentration of at most 20% by weight, more preferably at most 15% by weight, more preferably at most 10% by weight, more preferably at most 7% by weight, more preferably at most 5% by weight and most preferably at most 2% by weight based on the total weight of the positive electrode.

Structure of the Rechargeable Battery Cell

Advantageous developments of the rechargeable battery cell according to this disclosure are described below with regard to their structure.

In order to further improve the function of the rechargeable battery cell, a further advantageous development of the rechargeable battery cell according to this disclosure provides that the rechargeable battery cell comprises a plurality of negative electrodes and a plurality of positive electrodes, which are stacked alternately in the housing. Here, the positive electrodes and the negative electrodes are preferably each electrically separated from one another by separators.

The separator can be formed from a non-woven material, a membrane, a woven material, a knitted material, an organic material, an inorganic material or a combination thereof. Organic separators can consist of unsubstituted polyolefins (for example, polypropylene or polyethylene), partially to completely halogen-substituted polyolefins (for example, partially to completely fluorine-substituted, in particular PVDF, ETFE, PTFE), polyesters, polyamides or polysulfones. Separators that comprise a combination of organic and inorganic materials are, for example, glass fiber textile materials in which the glass fibers are provided with a suitable polymer coating. The coating preferably comprises a fluorine-comprising polymer such as polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene (ETFE), perfluoroethylene propylene (FEP), THV (terpolymer of tetrafluoroethylene, hexafluoroethylene and vinylidene fluoride), a perfluoroalkoxy polymer (PFA), aminosilane, polypropylene or polyethylene (PE). The separator can also be folded in the housing of the rechargeable battery cell, for example, in the form of so-called “Z-folding.” In this Z-folding, a strip-shaped separator is folded in a Z-like manner through or around the electrodes. Furthermore, the separator can also be formed as separator paper.

It is also within the scope of this disclosure for the separator to be able to be designed as a sheath, wherein each positive electrode or each negative electrode is enveloped by the sheath. The sheath can be formed from a non-woven material, a membrane, a woven material, a knitted material, an organic material, an inorganic material or a combination thereof.

A sheath on the positive electrode leads to more uniform ion migration and ion distribution in the rechargeable battery cell. The more even the ion distribution, in particular in the negative electrode, the higher the possible loading of the negative electrode with active material and, as a result, the usable capacity of the rechargeable battery cell. At the same time, risks are avoided that could be associated with uneven loading and the resulting deposition of the active metal. These advantages are particularly effective when the positive electrodes of the rechargeable battery cell are enveloped in the sheath.

The surface dimensions of the electrodes and the sheath can preferably be matched to one another such that the external dimensions of the sheath of the electrodes and the external dimensions of the unsheathed electrodes match at least in one dimension.

The surface area of the sheath can preferably be greater than the surface area of the electrode. In this case, the sheath extends beyond a boundary of the electrode. Two layers of the sheath covering the electrode on both sides can therefore be connected to one another at the edge of the positive electrode by an edge connection.

In a further advantageous embodiment of the rechargeable battery cell according to this disclosure, the negative electrodes have a sheath, while the positive electrodes have no sheath.

BRIEF DESCRIPTION OF THE DRAWINGS

The above-mentioned aspects of exemplary embodiments will become more apparent and will be better understood by reference to the following description of the embodiments taken in conjunction with the accompanying drawings, wherein:

FIG. 1 shows a first embodiment of a rechargeable battery cell according to this disclosure in a cross-sectional illustration;

FIG. 2 shows an electron microscope image of the three-dimensional porous structure of the metal foam of the first embodiment from FIG. 1 as a detailed illustration;

FIG. 3 shows a second embodiment of a rechargeable battery cell according to this disclosure in a cross-sectional illustration;

FIG. 4 shows a detail of the second embodiment from FIG. 3;

FIG. 5 shows a third embodiment of the rechargeable battery cell according to this disclosure in an exploded illustration;

FIG. 6 shows the potential in [V] of four test full cells when charging the negative electrodes with graphite 1, graphite 2, graphite 3 and graphite 4 as active electrode material as a function of capacity, during formation of a coating layer on the negative electrode;

FIG. 7 shows the discharge capacity as a function of the cycle number of three test full cells which comprise graphite 1, graphite 2 and graphite 3 as the active electrode material of the negative electrode;

FIG. 8 shows the potential in [V] of two test full cells when charging the negative electrodes with graphite 1 as the active electrode material as a function of capacity, during formation of a coating layer on the negative electrode, wherein one reference test full cell is filled with the reference electrolyte and one test full cell is filled with electrolyte 1;

FIG. 9 shows the discharge capacity as a function of the number of cycles of two test full cells which comprise graphite 1 as the active electrode material of the negative electrode, wherein one reference test full cell is filled with the reference electrolyte and one test full cell is filled with electrolyte 1;

FIG. 10 shows the potential in [V] of three half-cells when charging the negative electrodes with graphite 2, graphite 3 and graphite 4 as active electrode materials as a function of capacity, during formation of a coating layer on the negative electrode, wherein the half-cells are filled with the reference electrolyte;

FIG. 11 shows the potential in [V] of two test full cells when charging the negative electrodes with graphite 1 as the active electrode material as a function of capacity, during formation of a coating layer on the negative electrode, wherein one test full cell is filled with electrolyte 3 and one test full cell is filled with electrolyte 4;

FIG. 12 shows the potential in [V] during discharge as a function of the percentage charge of three test full cells which comprise graphite 1 as the active electrode material of the negative electrode and were filled with electrolytes 1, 3 and 4;

FIG. 13 shows the potential in [V] of three test full cells when charging the negative electrodes with blends of SiO_(x) 5.0%/graphite 3, SiO_(x) 17.3%/graphite 3 and SiO_(x) 24.0%/graphite 3 as electrode active materials as a function of capacity, during formation of a coating layer on the negative electrode;

FIG. 14 shows the discharge capacity of the first ten cycles during discharge as a function of the number of cycles of three test full cells which comprise blends of SiO_(x) 5.0%/graphite 3, SiO_(x) 17.3%/graphite 3 and SiO_(x) 24.0%/graphite 3 as the negative electrode active material;

FIG. 15 shows the potential in [V] of four test full cells when charging the negative electrodes with a blend of nano-silicon (5% by weight) and graphite 3 (95% by weight), a blend of nano-silicon (2.5% by weight) and graphite 1 (97.5% by weight), a blend of nano-silicon (5.0% by weight) and graphite 1 (95.0% by weight) and a blend of nano-silicon (10% by weight) and graphite 1 (90% by weight) as active electrode materials as a function of capacity, during formation of a coating layer on the negative electrode;

FIG. 16 shows the discharge capacity of the first ten cycles during discharge as a function of the number of cycles of four test full cells comprising a blend of nano-silicon (5% by weight) and graphite 3 (95% by weight), a blend of nano-silicon (2.5% by weight) and graphite 1 (97.5% by weight), a blend of nano-silicon (5.0% by weight) and graphite 1 (95.0% by weight) and a blend of nano-silicon (10% by weight) and graphite 1 (90% by weight) as the active electrode material of the negative electrode;

FIG. 17 shows the conductivity in [mS/cm] of electrolyte 1 as a function of the concentration;

FIG. 18 shows the conductivity in [mS/cm] of electrolyte 3 as a function of the concentration; and

FIG. 19 shows the conductivity in [mS/cm] of electrolyte 4 as a function of the concentration.

DESCRIPTION

The embodiments described below are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description. Rather, the embodiments are chosen and described so that others skilled in the art may appreciate and understand the principles and practices of this disclosure.

FIG. 1 shows a first embodiment of a rechargeable battery cell 2 according to this disclosure in a cross-sectional illustration. Said rechargeable battery cell 2 is designed as a prismatic cell and has a housing 1, among other things. Said housing 1 encloses an electrode array 3 which comprises three positive electrodes 4 and four negative electrodes 5. The positive electrodes 4 and the negative electrodes 5 are stacked alternately in the electrode array 3. The housing 1 can, however, also accommodate more positive electrodes 4 and/or negative electrodes 5. In general, it is preferred when the number of negative electrodes 5 is one greater than the number of positive electrodes 4. This has the consequence of the outer end faces of the electrode stack being formed by the electrode surfaces of the negative electrodes 5. The electrodes 4, 5 are connected to corresponding contacts 9, 10 of the rechargeable battery cell 2 via electrode connections 6, 7. The rechargeable battery cell 2 is filled with an SO₂-based electrolyte such that the electrolyte penetrates as completely as possible into all pores or cavities, in particular within the electrodes 4, 5. The electrolyte is not visible in FIG. 1. In the present embodiment, the positive electrodes 4 comprise an intercalation compound as an active material. This intercalation compound is LiCoMnO₄.

The electrodes 4, 5 are designed flat in the present embodiment, that is, as layers having a thickness that is smaller in relation to their surface area. They are each separated from one another by separators 11. The housing 1 of the rechargeable battery cell 2 is essentially designed cuboid, wherein the electrodes 4, 5 and the walls of the housing 1 shown in a sectional illustration extend perpendicular to the plane of the drawing and are essentially straight and flat. The rechargeable battery cell 2 can, however, also be designed as a winding cell in which the electrodes consist of thin layers that are wound up together with a separator material. The separators 11, on the one hand, separate the positive electrode 4 and the negative electrode 5 spatially and electrically and, on the other hand, are permeable to the ions of the active metal, among other things. In this way, large electrochemically effective surfaces are created, which enable a correspondingly high current yield.

The electrodes 4, 5 also have a discharge element which serves to enable the required electronically conductive connection of the active material of the respective electrode. Said discharge element is in contact with the active material involved in the electrode reaction of the respective electrode 4, 5 (not depicted in FIG. 1). The discharge element is designed in the form of a porous metal foam 18. The metal foam 18 extends over the thickness dimension of the electrodes 4, 5. The active material of the positive electrodes 4 and the negative electrodes 5 is incorporated into the pores of said metal foam 18 so that it fills its pores uniformly over the entire thickness of the metal structure. The positive electrodes 4 comprise a binder to improve the mechanical strength. This binder is a fluoropolymer. The negative electrodes 5 comprise carbon as an active material in a form suitable as an insertion material for the absorption of lithium ions. The structure of the negative electrode 5 is similar to that of the positive electrode 4.

FIG. 2 shows an electron microscope image of the three-dimensional porous structure of the metal foam 18 of the first embodiment from FIG. 1. On the basis of the specified scale, it can be seen that the pores P have an average diameter of more than 100 μm, that is, are relatively large. This metal foam is a metal foam made of nickel.

FIG. 3 shows a second embodiment of a rechargeable battery cell 20 according to this disclosure in a cross-sectional illustration. Said second embodiment differs from the first embodiment shown in FIG. 1 in that the electrode array comprises a positive electrode 23 and two negative electrodes 22. They are each separated from one another by separators 21 and surrounded by a housing 28. The positive electrode 23 has a discharge element 26 in the form of a planar metal foil, to which the active material 24 of the positive electrode 23 is applied on both sides. The negative electrodes 22 also comprise a discharge element 27 in the form of a planar metal foil, to which the active material 25 of the negative electrode 22 is applied on both sides. Alternatively, the planar discharge elements of the edge electrodes, that is, of the electrodes that close off the electrode stack, can only be coated with active material on one side. The non-coated side faces the wall of the housing 28. The electrodes 22, 23 are connected to corresponding contacts 31, 32 of the rechargeable battery cell 20 via electrode connections 29, 30.

FIG. 4 shows the planar metal foil which serves as a discharge element 26, 27 for the positive electrodes 23 and the negative electrodes 22 in the second embodiment from FIG. 3. This metal foil has a perforated or mesh-like structure having a thickness of 20 μm.

FIG. 5 shows a third embodiment of a rechargeable battery cell 40 according to this disclosure in an exploded illustration. This third embodiment differs from the two embodiments explained above in that the positive electrode 44 is enveloped by a sheath 13. In this case, a surface area of the sheath 13 is greater than a surface area of the positive electrode 44, the boundary 14 of which is shown in FIG. 5 as a dashed line. Two layers 15, 16 of the sheath 13 that cover the positive electrode 44 on both sides are connected to one another at the circumferential edge of the positive electrode 44 by an edge connection 17. The two negative electrodes 45 are not enveloped. The electrodes 44 and 45 can be contacted via the electrode connections 46 and 47.

EXAMPLE 1 Preparation of a Reference Electrolyte

A reference electrolyte used for the examples described below was produced according to the method described in patent specification EP 2 954 588 B1 (hereinafter referred to as [V2]). First, lithium chloride (LiCl) was dried under vacuum at 120° C. for three days. Aluminum particles (Al) were dried under vacuum for two days at 450° C. LiCl, aluminum chloride (AlCl₃) and Al were mixed together in an AlCl₃:LiCl:Al molar ratio of 1:1.06:0.35 in a glass bottle having an opening to allow gas to escape. This blend was thereafter heat-treated in stages to produce a molten salt. After cooling, the salt melt formed was filtered, then cooled to room temperature and finally SO₂ was added until the desired molar ratio of SO₂ to LiAlCl₄ was formed. The reference electrolyte thus formed had the composition LiAlCl₄*x SO₂, wherein x is dependent on the amount of SO₂ supplied.

EXAMPLE 2 Preparation of Four Embodiments 1, 2, 3 and 4 of an SO₂-Based Electrolyte for a Battery Cell

Four embodiments 1, 2, 3 and 4 of the SO₂-based electrolyte were prepared for the experiments described below (hereinafter referred to as electrolytes 1, 2, 3 and 4). For this purpose, four different first conducting salts according to formula (I) were initially prepared using a manufacturing process described in the following documents [V3], [V4] and [V5]:

-   -   [V3] “I. Krossing, Chem. Eur. 1 2001, 7, 490;     -   [V4] S. M. Ivanova et al., Chem. Eur. 1 2001, 7, 503;     -   [V5] Tsujioka et al., J. Electrochem. Soc., 2004, 151, A1418”

These four different, first conducting salts according to formula (I) are referred to below as compounds 1, 2, 3 and 4. They come from the family of polyfluoroalkoxyaluminates and were prepared in hexane according to the following reaction equation, starting from LiAlH₄ and the corresponding alcohol R—OH with R¹=R²=R³=R⁴.

As a result, compounds 1, 2, 3 and 4 shown below were formed using the sum and structural formulas:

Compounds 1, 2, 3 and 4 were first recrystallized for purification. As a result, residues of the educt LiAlH₄ were removed from the first conducting salt, since said educt could possibly lead to the formation of sparks with possibly existing traces of water in SO₂.

Compounds 1, 2, 3 and 4 were then dissolved in SO₂. It was found that compounds 1, 2, 3 and 4 dissolve well in SO₂.

The preparation of electrolytes 1, 2, 3 and 4 was performed at low temperature or under pressure according to process steps 1 to 4 listed below:

-   -   1) receiving of the respective compound 1, 2, 3 and 4 in a         pressure piston each with a riser pipe,     -   2) evacuation of the pressure pistons,     -   3) inflow of liquid SO₂, and     -   4) repetition of steps 2+3 until the target amount of SO₂ was         added.

The respective concentration of compounds 1, 2, 3 and 4 in electrolytes 1, 2, 3 and 4 was 0.6 mol/L (molar concentration based on 1 liter of the electrolyte), unless otherwise described in the description of the experiment. The experiments described below were performed using electrolytes 1, 2, 3 and 4 and the reference electrolyte.

EXAMPLE 3 Production of Test Full Cells

The test full cells used in the experiments described below are rechargeable battery cells having two negative electrodes and one positive electrode, each separated by a separator. The positive electrodes had an active material (named in the respective experiment), a conductivity mediator and a binder.

The examined negative electrodes comprised an active material, which is named in the respective experiment description. The negative electrodes can also comprise a binder and/or a conductivity additive. The discharge element of the positive and negative electrodes was made of nickel. Tables 3a and 3b show which active materials were examined for the negative electrodes.

TABLE 3a Investigated Graphites as Negative Electrode Active Materials Mean Grain Size Spec. Surface Name Type D50 [μm] [m²/g] Graphite 1 Synthetic graphite 22.4 3.7 Graphite 2 Synthetic graphite 20.2 1.8 Graphite 3 Synthetic graphite 17.0 1.8 Graphite 4 Synthetic graphite 22.1 5.4

TABLE 3b Investigated Blends Comprising Silicon as Active Materials of the Negative Electrode Name Type SiOx 5.0%/graphite 3 Blend of SiOx (5% by weight) and graphite 3 (95% by weight) SiOx 17.3%/graphite 3 Blend of SiOx (17.3% by weight)/ graphite 3 (82.7% by weight) SiOx 24%/graphite 3 Blend of SiOx (24% by weight)/ graphite 3 (76% by weight) Nano-Si 5.0%/graphite 3 Blend of nano-silicon (5% by weight) and graphite 3 (95% by weight Si) Nano-Si 2.5%/graphite 1 Blend of nano-silicon (2.5% by weight) and graphite 1 (97.5% by weight) Nano-Si 5.0%/graphite 1 Blend of nano-silicon (5% by weight) and graphite 1 (95% by weight) Nano-Si 10%/graphite 1 Blend of nano-silicon (10% by weight) and graphite 1 (90% by weight)

The test full cells were each filled with the electrolyte required for the experiments, that is, either with the reference electrolyte or electrolytes 1, 2, 3 or 4.

Several, that is, two to four, identical test whole cells were produced for each experiment. The results presented in the experiments are each mean values from the measured values obtained for the identical test full cells.

EXAMPLE 4 Measurement in Test Full Cells Coating Layer Capacity:

The capacity consumed in the first cycle to form a coating layer on the negative electrode is an important criterion for the quality of a battery cell. This coating layer is formed on the negative electrode when the test full cell is charged for the first time. Lithium ions are irreversibly consumed for this formation of a coating layer (coating layer capacity), so that the test full cell has less cyclic capacity available for the subsequent cycles. The coating layer capacity in % of the theory that was used to form the coating layer on the negative electrode is calculated according to the following formula:

Coating layer capacity [in % of the theory]=(Q_(lad)(xmAh)−Q _(ent)(ymAh))/Q _(NEL)

Q_(lad) describes the amount of charge specified in the respective experiment in mAh; Q_(ent) describes the amount of charge in mAh that was obtained when the test full cell was subsequently discharged. Q_(NEL) is the theoretical capacity of the negative electrode used. The theoretical capacity is calculated, for example, in the case of graphite, to a value of 372 mAh/g.

The nominal capacity is obtained by subtracting the coating layer capacity (=Q_(lad)(x mAh)−Q_(ent) (y mAh)) from the theoretical capacity of the positive electrode.

Discharge Capacity:

For measurements in test full cells, for example, the discharge capacity is determined from the number of cycles. For this purpose, the test full cells are charged with a certain charge current intensity up to a certain upper potential. The corresponding upper potential is held until the charge current has dropped to a certain value. The discharge then takes place with a certain discharge current intensity up to a certain discharge potential. This charging method is called I/U charging. This process is repeated depending on the desired number of cycles.

The upper potentials or the discharge potential and the respective charge or discharge current intensities are given in the experiments. The value to which the charge current must have dropped is also described in the experiments.

The term “upper potential” is used as a synonym for the terms “charge potential,” “charge voltage,” “end-of-charge voltage” and “upper potential limit.” The terms denote the voltage/potential up to which a cell or battery is charged with the aid of a battery charger.

The battery is preferably charged at a current rate of C/2 and at a temperature of 22° C. With a charge or discharge rate of 1 C, by definition, the nominal capacity of a cell is charged or discharged in one hour. A charge rate of C/2 means a charge time of 2 hours.

The term “discharge potential” is used synonymously with the term “lower cell voltage.” This describes the voltage/potential up to which a cell or battery is discharged with the aid of a battery charger.

The battery is preferably discharged at a current rate of C/2 and at a temperature of 22° C.

The discharge capacity is obtained from the discharge current and the time until the criteria for ending the discharge are fulfilled. The associated figures show mean values for the discharge capacities as a function of the number of cycles. These mean values of the discharge capacities are often normalized to the maximum capacity that was achieved in the respective experiment and expressed in percent of the nominal capacity.

Experiment 1: Test Full Cells Having Different Graphites as the Positive Electrode Active Material

Experiments in test full cells according to Example 3 were performed using various graphites as active materials of the negative electrode. On the one hand, the coating layer capacities (graphite 1, 2, 3 and 4) and, on the other hand, the discharge capacities (graphite 1, 2 and 3) were determined. The test full cells were filled with electrolyte 1 described in Example 2.

The test full cells comprised negative electrodes having the synthetic graphites described in Table 3a, that is, using graphite 1, graphite 2, graphite 3 or graphite 4 as an active material. The positive electrodes comprised lithium nickel manganese cobalt oxide (NMC622) (graphite 1, 2 and 3) and lithium iron phosphate (graphite 4) as the active material.

FIG. 6 shows the potential in volts of the test full cells when charging the negative electrode as a function of capacity, which is related to the theoretical capacity of the negative electrode. The four curves depicted show averaged results of several experiments with the test whole cells described above. The curve of the test full cell having graphite 4 is at slightly lower potentials due to the different active material of the positive electrode. First, the test full cells were charged with a current of 15 mA until a capacity of 125 mAh (Q_(lad)) was reached. The test full cells were then discharged at 15 mA until a potential of 2.5 volts was reached. The discharge capacity (Q_(ent)) was determined.

The determined coating layer capacities [in % of the theoretical capacity of the negative electrode] are 6.58% for graphite 1, 4.29% for graphite 2, 5.32% for graphite 3 and 7.27% for graphite 4. These are excellent values compared to existing systems in organic electrolytes.

The discharge capacity was determined in further cycles using the test full cells comprising graphite 1, 2 and 3. To determine the discharge capacities (see Example 4), the test full cells were charged with a current intensity of 100 mA up to an upper potential of 4.4 volts. The corresponding upper potential was held until the charge current had dropped to 40 mA. The discharge then took place with a current intensity of 100 mA up to a discharge potential of 2.5 volts.

FIG. 7 shows mean values for the discharge capacities normalized to 100% of the starting capacity of the three test full cells as a function of the number of cycles. These mean values of the discharge capacities are expressed as a percentage of the nominal capacity. The test full cells having different graphites show a very stable behavior of the discharge capacities over the number of cycles. 96% of the discharge capacity is still achieved in cycle 250 in the test full cells having graphite 1 and graphite 3. The test full cell having graphite 2 still achieved 93%.

Experiment 2: Graphite 1 as the Active Material of the Negative Electrode in Test Full Cells Using Electrolyte 1 and, in Comparison, in Test Full Cells Using Reference Electrolyte

Experiments in two test full cells according to Example 3 were performed using graphite 1 as the anode material. The one test full cell was filled with electrolyte 1 described in Example 2, the other test full cell comprised a reference electrolyte having the composition LiAlCl₄×6SO₂. The positive electrodes comprised lithium nickel manganese cobalt oxide (NMC622) as an active material.

On the one hand, the coating layer capacities and on the other hand, the discharge capacities were determined.

FIG. 8 shows the potential in volts of the test full cells when charging the negative electrode as a function of capacity, which is related to the theoretical capacity of the negative electrode. The two curves depicted show averaged results of several experiments with the test whole cells described above. First, the test full cells were charged with a current of 15 mA until a capacity of 125 mAh (Q_(lad)) was reached. The test full cells were then discharged at 15 mA until a potential of 2.5 volts was reached. The discharge capacity (Q_(ent)) was determined.

The coating layer capacities determined [in % of the theoretical capacity of the negative electrode] are 6.58% for graphite 1 in the test full cell using electrolyte 1 and 8.30% for graphite 1 in the test full cell using the reference electrolyte. The advantage of electrolyte 1 in combination with graphite 1 is shown in a significantly reduced coating layer capacity.

The discharge capacities were determined in further cycles using the same test full cells. To determine the discharge capacities (see Example 4), the test full cells were charged with a current intensity of 100 mA up to an upper potential of 4.4 volts. The corresponding upper potential was held until the charge current had dropped to 40 mA. The discharge then took place with a current intensity of 100 mA up to a discharge potential of 2.5 volts.

FIG. 9 shows mean values for the discharge capacities normalized to 100% of the starting capacity of the two test full cells as a function of the number of cycles. These mean values of the discharge capacities are expressed as a percentage of the nominal capacity.

The test full cells having the different electrolytes show a different behavior of the discharge capacities over the number of cycles. In the test full cells with graphite 1 in electrolyte 1, 98.4% of the discharge capacity is still reached in cycle 280 with an almost horizontal profile. The test full cell with graphite 1 in reference electrolyte still achieved 96.8% with a slightly further downward trend.

Experiment 3: Cover Layer Formation on Graphite 2, Graphite 3 and Graphite 4 in Half-Cells Using Reference Electrolyte

For preliminary tests to investigate the coating layer capacity, half-cell experiments were performed at room temperature both with negative electrodes which comprised graphite 2 and graphite 3 as active material, and with a negative electrode, which comprised graphite 4 as an active material. The half-cells were filled with a reference electrolyte of the composition LiAlCl₄×1.5 SO₂ and had a lithium electrode as the reference electrode. Such electrochemical half-cell experiments are standard experiments for testing the performance data of electrodes due to their simple structure and the associated low experimental effort.

The half-cells were charged and discharged a plurality of times with a current intensity of 10 mA (corresponding to 1 C to the practical capacity). The coating layer capacity was calculated from the capacity loss of the first three cycles.

FIG. 10 shows the coating layer curves and the associated coating layer capacities of the two half-cell experiments. The coating layer capacity in the reference electrolyte is 12.1% for the half-cell having graphite 2, 10.3% for graphite 3 and 15.5% for graphite 4 of the theoretical capacity of the negative electrode. These values are significantly higher than the data determined in Experiment 1 for the same graphites in electrolyte 1.

Experiment 4: Graphite 1 as the Active Material of the Negative Electrode in Test Full Cells Using Electrolyte 1, Electrolyte 3 and Electrolyte 4

Various experiments were performed to investigate electrolytes 1, 3 and 4 in combination with graphite 1 as the active material of the negative electrode. On the one hand, the coating layer capacities of electrolytes 3 and 4 were determined and, on the other hand, discharge capacities in all three electrolytes 1, 3 and 4 were determined.

Two test full cells were filled with electrolytes 3 and 4 described in Example 2 to determine the coating layer capacity. The two test full cells comprised graphite 1 as the active material of the negative electrode. The positive electrodes had lithium nickel manganese cobalt oxide (NMC622) as an active material.

FIG. 11 shows the potential in volts of the test full cells when charging the negative electrode as a function of capacity, which is related to the theoretical capacity of the negative electrode. The two curves depicted show averaged results of several experiments with the test whole cells described above. First, the test full cells were charged with a current of 15 mA until a capacity of 125 mAh (Q_(lad)) was reached. The test full cells were then discharged at 15 mA until a potential of 2.5 volts was reached. The discharge capacity (Q_(ent)) was determined.

The coating layer capacities determined [in % of the theoretical capacity of the negative electrode] are 17.77% in electrolyte 3 and 20.02% in electrolyte 4. Very good operation of a battery cell having these electrolytes is also possible with the somewhat higher values of the coating layer capacity in electrolytes 3 and 4.

For the discharge experiments, three test full cells according to Example 3 were filled with electrolytes 1, 3 and 4 described in Example 2. The test full cells had lithium nickel manganese cobalt oxide (NMC) as the active material of the positive electrode and graphite 1 as the active material of the negative electrode. To determine the discharge capacities (see example 4), the test full cells were charged with a current intensity of 15 mA up to a capacity of 125 mAh. The discharge then took place with a current intensity of 15 mA up to a discharge potential of 2.5 volts.

FIG. 12 shows the potential profile during the discharge over the discharged amount of charge in % [% of the maximum charge (discharge)]. All test full cells show a flat discharge curve, which is necessary for good operation of a battery cell.

Experiment 5: Test Full Cells Having Blends of SiO_(x) 5.0%/Graphite 3, SiO_(x) 17.3%/Graphite 3 and SiO_(x) 24.0%/Graphite 3 as Active Materials of the Negative Electrode

As can be seen in Table 3b, the term SiO_(x) 5%/graphite 3 denotes blends of SiO_(x) (5% by weight) and graphite 3 (95% by weight), wherein SiO_(x) consists of a blend of the components Si, SiO and SiO₂. The further described SiOx/graphite 3 blends have an SiO content of 17.3% by weight SiO or 24.0% by weight SiO and the corresponding amounts of graphite 3.

The three different blends were used in three test full cells according to Example 3 as the active material of the negative electrode, and experiments were performed. On the one hand, the coating layer capacities and on the other hand, the discharge capacities were determined. The test full cells were filled with electrolyte 1 described in Example 2. The positive electrodes comprised lithium nickel manganese cobalt oxide as an active material.

FIG. 13 shows the potential in volts of the three test full cells when charging the negative electrode as a function of capacity, which is related to the theoretical capacity of the negative electrode. The curves depicted show averaged results of several experiments with the test whole cells described above. First, the test full cells were charged with a current of 15 mA until a capacity of 125 mAh (Q_(lad)) was reached. The test full cells were then discharged at 15 mA until a potential of 2.8 volts was reached. The discharge capacity (Q_(ent)) was determined.

The coating layer capacities determined [in % of the theoretical capacity of the negative electrode] are 12.69% for the SiO_(x) 5.0%/graphite 3 blend, 15.29% for the SiO_(x) 17.3%/graphite 3 blend and 14.41% for the SiO_(x) 24.0%/graphite 3 blend.

The discharge capacity was determined in ten further cycles using the same test full cells. To determine the discharge capacities (see Example 4), the test full cells were charged with a current intensity of 40 mA up to an upper potential of 4.4 volts. The discharge then took place with a current intensity of 40 mA up to a discharge potential of 2.8 volts. FIG. 14 shows mean values for the discharge capacities for the 10 cycles normalized to 100% of the starting capacity of the test full cells as a function of the number of cycles. These mean values of the discharge capacities are expressed as a percentage of the nominal capacity. All three cells show a flat profile of the discharge capacity.

Experiment 6: Test Full Cells Having Nano-Silicon/Graphite as the Active Material of the Negative Electrode

Experiments in test full cells according to Example 3 were performed using the nano-silicon/graphite blends mentioned in Table 3b as active materials of the negative electrode. On the one hand, the coating layer capacities and on the other hand, the discharge capacities were determined. The test full cells were filled with electrolyte 1 described in Example 2.

The four test full cells comprised negative electrodes having either a blend of nano-silicon (5% by weight) and graphite 3 (95% by weight) or a blend of nano-silicon (2.5% by weight) and graphite 1 (97.5% by weight) or a blend of nano-silicon (5.0% by weight) and graphite 1 (95.0% by weight) or a blend of nano-silicon (10% by weight) and graphite 1 (90% by weight). The positive electrodes comprised lithium nickel manganese cobalt oxide as an active material.

FIG. 15 shows the potential in volts of the test full cells when charging the negative electrode as a function of capacity, which is related to the theoretical capacity of the negative electrode. The four curves depicted show averaged results of several experiments with the test whole cells described above. First, the test full cells were charged with a current of 15 mA until a capacity of 125 mAh (Q_(lad)) was reached. The test full cells were then discharged at 15 mA until a potential of 2.8 volts was reached. The discharge capacity (Q_(ent)) was determined.

The coating layer capacities determined [in % of the theoretical capacity of the negative electrode] are 12.47% for the blend of nano-silicon (5% by weight) and graphite 3 (95% by weight), 9.91% for the blend of nano-silicon (2.5% by weight) and graphite 1 (97.5% by weight), 11.63% for the blend of nano-silicon (5.0% by weight) and graphite 1 (95.0% by weight) and 14.77% for the blend of nano-silicon (10% by weight) and graphite 1 (90% by weight).

The discharge capacities were determined in further ten cycles using the same test full cells. To determine the discharge capacities (see Example 4), the test full cells were charged with a current intensity of 40 mA up to an upper potential of 4.4 volts. The discharge then took place with a current intensity of 40 mA up to a discharge potential of 2.8 volts. FIG. 16 shows mean values for the discharge capacities for the 10 cycles of the three test full cells as a function of the number of cycles. These mean values of the discharge capacities are expressed as a percentage of the nominal capacity. All four cells show a flat profile of the discharge capacity.

Experiment 7: Determination of the Conductivities of Electrolytes 1, 3 and 4

To determine the conductivity, electrolytes 1, 3 and 4 were prepared using different concentrations of compounds 1, 3 and 4. The conductivities of the electrolytes were determined using a conductive measurement method for each concentration of the various compounds. After temperature control, a two-electrode sensor was held touching in the solution and measured in a measuring range of 0-50 mS/cm. During the measurements, it was noted that the sensor can react with the SO₂-comprising electrolyte solution.

FIG. 17 shows the conductivity of electrolyte 1 as a function of the concentration of compound 1. A maximum of the conductivity can be seen at a concentration of compound 1 of 0.6 mol/L-0.7 mol/L having a value of approx. 37.9 mS/cm. In comparison, the organic electrolytes known from the prior art, such as LP30 (1 M LiPF₆/EC-DMC (1:1 weight)) have a conductivity of only approx. 10 mS/cm.

FIGS. 18 (electrolyte 3) and 19 (electrolyte 4) show the conductivity values for electrolytes 3 and 4 determined for the different concentrations.

With electrolyte 4, a maximum of 18 mS/cm is achieved at a conducting salt concentration of 1 mol/L. Electrolyte 3 shows its highest conductivity of 0.5 mS/cm at a conducting salt concentration of 0.6 mol/L. Although electrolyte 3 shows a lower conductivity, as in experiment 4, charging or discharging of a test full cell is quite possible.

Experiment 8: Low Temperature Behavior

Two test full cells according to example 3 were produced in order to determine the low-temperature behavior of electrolyte 1 in comparison to the reference electrolyte. One test full cell was filled with reference electrolyte of the composition LiAlCl₄*6SO₂ and the other test full cell with electrolyte 1. The test full cell having the reference electrolyte comprised lithium iron phosphate (LEP) as the active material, the test cell having electrolyte 1 comprised lithium nickel manganese cobalt oxide (NMC) as the active material of the positive electrode. Both test full cells comprised graphite 1 as the active material of the negative electrode. The test full cells were charged to 3.6 volts (LEP) or 4.4 volts (NMC) at 20° C. and discharged again to 2.5 volts at the respective temperature to be investigated. The discharge capacity reached at 20° C. was rated as 100%. The temperature for the discharge was lowered in temperature steps of 10° K. The discharge capacity obtained was described in % of the discharge capacity at 20° C. Since the low-temperature discharges are almost independent of the active materials used for the positive and negative electrodes, the results can be transferred to all combinations of active materials. Table 4 shows the results.

TABLE 4 Discharge Capacities as a Function of the Temperature Discharge Capacity Discharge Capacity of Temperature of Electrolyte 1 the Reference Electrolyte 20° C. 100%  100%  10° C. 99% 99% 0° C. 95% 46% −10° C. 89% 21% −20° C. 82% n/a −30° C. 73% n/a −35° C. 68% n/a −40° C. 61% n/a

The test full cell having electrolyte 1 shows very good low-temperature behavior. At −20° C., 82% of the capacity is reached, at −30° C., 73%. Even at a temperature of −40° C., 61% of the capacity can still be discharged. In contrast, the test full cell having the reference electrolyte only shows a discharge capacity down to −10° C. A capacity of 21% is achieved here. The cell having the reference electrolyte can no longer be discharged at lower temperatures.

While exemplary embodiments have been disclosed hereinabove, the present invention is not limited to the disclosed embodiments. Instead, this application is intended to cover any variations, uses, or adaptations of this disclosure using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims. 

What is claimed is:
 1. A rechargeable battery cell, comprising: an active metal; at least one positive electrode; at least one negative electrode comprising an active material selected from the group consisting of an insertion material made of carbon, an alloy-forming active material, an intercalation material which does not comprise carbon, and a conversion active material; an SO₂ based electrolyte comprising a first conducting salt which has the formula (I),

wherein: M is a metal selected from the group consisting of alkali metals, alkaline earth metals, metals of group 12 of the periodic table of the elements, and aluminum; x is an integer from 1 to 3; R¹, R², R³ and R⁴ are selected independently of one another from the group consisting of C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₂-C₁₀ alkynyl, C₃-C₁₀ cycloalkyl, C₆-C₁₄ aryl and C₅-C₁₄ heteroaryl; and Z is aluminum or boron.
 2. The rechargeable battery cell according to claim 1, wherein the insertion material made of carbon is selected from the group consisting of: graphite, natural graphite, synthetic graphite, graphitized mesocarbon microbeads, carbon coated graphite, and amorphous carbon.
 3. The rechargeable battery cell according to claim 2, wherein the natural graphite comprises flake-shaped or rounded natural graphite and the synthetic graphite comprises mesophase graphite.
 4. The rechargeable battery cell according to claim 1, wherein the alloy-forming active material is selected from the group consisting of lithium-storing metals and metal alloys or from the group consisting of oxides of lithium-storing metals and metal alloys.
 5. The rechargeable battery cell according to claim 4, wherein the lithium-storing metals and metal alloys are selected from the group consisting of Si, Ge, Sn, SnCo_(x)C_(y) and SnSi_(x), and the oxides of lithium-storing metals and metal alloys are selected from the group consisting of SnO_(x), SiO_(x) and oxidic glasses of Sn, Si.
 6. The rechargeable battery cell according to claim 1, wherein the alloy-forming active material is formed from silicon or from silicon oxides or from blends of silicon and silicon oxides.
 7. The rechargeable battery cell according to claim 1, wherein the negative electrode comprises at least one alloy-forming anode active material.
 8. The rechargeable battery cell according to claim 7, wherein the alloy-forming anode active material forms an alloy with lithium, in combination with at least one insertion material made of carbon, combinations of silicon and/or silicon oxides and graphite.
 9. The rechargeable battery cell according to claim 1, wherein the intercalation material is a lithium titanate.
 10. The rechargeable battery cell according to claim 9, wherein the lithium titanate comprises Li₄Ti₅O₁₂.
 11. The rechargeable battery cell according to claim 1, wherein the conversion active material is selected from: the group consisting of manganese oxides (MnO_(x)), iron oxides (FeO_(x)), cobalt oxides (CoO_(x)), nickel oxides (NiO_(x)) and copper oxides (CuO_(x)), or the group consisting of magnesium hydride (MgH₂), titanium hydride (TiH₂), aluminum hydride (AlH₃) and boron-, aluminum- and magnesium-based ternary hydrides.
 12. The rechargeable battery cell according to claim 1, wherein the positive electrode comprises as active material at least one compound having the composition A_(x)M′_(y)M″_(z)O_(a), wherein: A is at least one metal selected from the group consisting of the alkali metals, the alkaline earth metals, the metals of group 12 of the periodic table, and aluminum; M′ is at least one metal selected from the group consisting of the elements Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn; M″ is at least one element selected from the group consisting of the elements of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16 of the periodic table of the elements; x and y independently of one another are numbers greater than 0; z is a number greater than or equal to 0; and a is a number greater than
 0. 13. The rechargeable battery cell according to claim 12, wherein the compound has the composition Li_(x)M′_(y)M″_(z)O_(a), wherein M′ is manganese and M″ is cobalt.
 14. The rechargeable battery cell according to claim 13, wherein x, y and z are equal to 1 and a is equal to
 4. 15. The rechargeable battery cell according to claim 12, wherein the compound has the composition Li_(x)M′_(y)M″_(z)O_(a), wherein M′ comprises nickel and manganese and M″ is cobalt and the composition has the formula Li_(x)Ni_(y1)Mn_(y2)Co_(z)O_(a).
 16. The rechargeable battery cell according to claim 12, wherein the compound has the composition Li_(x)M′_(y)M″¹ _(z1)M″² _(z2)O₄, wherein M″² is phosphorus and z2 has the value
 1. 17. The rechargeable battery cell according to claim 16, wherein the compound has the composition Li_(x)M′_(y)M″¹ _(z1)PO₄, wherein M′ is iron and M″¹ _(z1) is manganese.
 18. The rechargeable battery cell according to claim 17, wherein the compound has the composition Li(Fe_(0.3)Mn_(0.7))PO₄.
 19. The rechargeable battery cell according to claim 1, wherein R¹, R², R³ and R⁴ are selected independently of one another from the group consisting of: C₁-C₆ alkyl; C₂-C₆ alkenyl; C₂-C₆ alkynyl; C₃-C₆ cycloalkyl; phenyl; and C₅-C₇ heteroaryl.
 20. The rechargeable battery cell according to claim 19, wherein: the C₁-C₆ alkyl comprises C₂-C₄ alkyl; the C₂-C₆ alkenyl comprises C₂-C₄ alkenyl; and the C₂-C₆ alkynyl comprises C₂-C₄ alkynyl.
 21. The rechargeable battery cell according to claim 20, wherein: the C₂-C₄ alkyl is selected from the group consisting of 2-propyl, methyl and ethyl; and the C₂-C₄ alkenyl is selected from the group consisting of ethenyl and propenyl.
 22. The rechargeable battery cell according to claim 1, wherein at least one of R¹, R², R³ and R⁴ is substituted by at least one fluorine atom and/or by at least one chemical group, wherein the chemical group is selected from the group consisting of C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, phenyl and benzyl.
 23. The rechargeable battery cell according to claim 1, wherein at least one of R¹, R², R³ and R⁴ is a CF₃ group or an OSO₂CF₃ group.
 24. The rechargeable battery cell according to claim 1, wherein the first conducting salt is selected from the group consisting of:


25. The rechargeable battery cell according to claim 1, wherein the electrolyte comprises a second conducting salt different from the first conducting salt.
 26. The rechargeable battery cell according to claim 25, wherein the second conducting salt is an alkali metal compound.
 27. The rechargeable battery cell according to claim 26, wherein the alkali metal compound is a lithium compound selected from the group consisting of an aluminate, a halide, an oxalate, a borate, a phosphate, an arsenate and a gallate.
 28. The rechargeable battery cell according to claim 25, wherein the second conducting salt is a lithium tetrahaloaluminate.
 29. The rechargeable battery cell according to claim 28, wherein the lithium tetrahaloaluminate is lithium tetrachloroaluminate.
 30. The rechargeable battery cell according to claim 1, wherein the electrolyte comprises at least one additive.
 31. The rechargeable battery cell according to claim 30, wherein the additive of the electrolyte is selected from the group consisting of vinylene carbonate and its derivatives, vinylethylene carbonate and its derivatives, methylethylene carbonate and its derivatives, lithium (bisoxalato)borate, lithium difluoro(oxalato)borate, lithium tetrafluoro(oxalato)phosphate, lithium oxalate, 2-vinylpyridine, 4-vinylpyridine, cyclic exomethylene carbonates, sultones, cyclic and acyclic sulfonates, acyclic sulfites, cyclic and acyclic sulfinates, organic esters, inorganic acids, acyclic and cyclic alkanes, which acyclic and cyclic alkanes have a boiling point of at least 36° C. at 1 bar, aromatic compounds, halogenated cyclic and acyclic sulfonylimides, halogenated cyclic and acyclic phosphate esters, halogenated cyclic and acyclic phosphines, halogenated cyclic and acyclic phosphites, halogenated cyclic and acyclic phosphazenes, halogenated cyclic and acyclic silylamines, halogenated cyclic and acyclic halogenated esters, halogenated cyclic and acyclic amides, halogenated cyclic and acyclic anhydrides, and halogenated organic heterocycles.
 32. The rechargeable battery cell according to claim 1, wherein the electrolyte comprises: (i) 5 to 99.4% by weight sulfur dioxide; (ii) 0.6 to 95% by weight of the first conducting salt; (iii) 0 to 25% by weight of the second conducting salt; and (iv) 0 to 10% by weight of the additive; based on the total weight of the electrolyte composition.
 33. The rechargeable battery cell according to claim 1, wherein the molar concentration of the first conducting salt is in the range selected from the group consisting of from 0.01 mol/L to 10 mol/L, from 0.05 mol/L to 10 mol/L, from 0.1 mol/L to 6 mol/L and from 0.2 mol/L to 3.5 mol/L, based on the total volume of the electrolyte.
 34. The rechargeable battery cell according to claim 1, wherein the electrolyte has a molar concentration of SO₂ per mole of conducting salt selected from the group consisting of at least 0.1 mol SO₂, at least 1 mol SO₂, at least 5 mol SO₂, at least 10 mol SO₂ and at least 20 mol SO₂.
 35. The rechargeable battery cell according to claim 1, wherein the active metal comprises: an alkali metal; an alkaline earth metal; a metal from group 12 of the periodic table; or aluminum.
 36. The rechargeable battery cell according to claim 35, wherein the alkali metal is lithium or sodium, the alkaline earth metal is calcium, and the metal from group 12 of the periodic table is zinc.
 37. The rechargeable battery cell according to claim 1, wherein the positive electrode comprises at least one metal compound selected from the group consisting of a metal oxide, a metal halide and a metal phosphate.
 38. The rechargeable battery cell according to claim 37, wherein the metal of the metal compound is a transition metal of atomic numbers 22 to 28 of the periodic table of the elements.
 39. The rechargeable battery cell according to claim 38, wherein the metal of the metal compound is cobalt, nickel, manganese or iron.
 40. The rechargeable battery cell according to claim 1, wherein the positive electrode comprises at least one metal compound having the chemical structure of a spinel, a layered oxide, a conversion compound or a polyanionic compound.
 41. The rechargeable battery cell according to claim 1, wherein the positive electrode and/or the negative electrode have a discharge element, which is formed (i) planar in the form of a metal sheet or a metal foil, or (ii) three-dimensional in the form of a porous metal structure.
 42. The rechargeable battery cell according to claim 41, wherein the porous metal structure comprises a metal foam.
 43. The rechargeable battery cell according to claim 1, wherein the positive electrode and/or the negative electrode comprises at least one binder, the binder comprising: a fluorinated binder, or a polymer which is built up from monomeric structural units of a conjugated carboxylic acid or from the alkali, alkaline earth or ammonium salt of said conjugated carboxylic acid or from a combination thereof, or a polymer based on monomeric styrene and butadiene structural units, or a binder from the group of carboxymethyl celluloses, wherein the binder is present in a concentration by weight selected from the group consisting of at most 20%, at most 15%, at most 10%, at most 7%, at most 5% and at most 2% based on the total positive electrode weight.
 44. The rechargeable battery cell according to claim 43, wherein the fluorinated binder is a polyvinylidene fluoride and/or a terpolymer made of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride.
 45. The rechargeable battery cell according to claim 1, wherein the at least one positive electrode comprises a plurality of electrodes and the at least one negative electrode comprises a plurality of negative electrodes, wherein the positive and negative electrodes are stacked alternately in the housing.
 46. The rechargeable battery cell according to claim 45, wherein the positive and negative electrodes are separated from one another by separators. 